Organic electroluminescent materials and devices

ABSTRACT

A novel compound is disclosed which includes a ligand LA of Formula II,wherein:ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;X1 to X4 are each independently selected from the group consisting of C, N, and CR;at least one pair of adjacent X1 to X4 are each C and fused to Formula V where indicated by “”; X5 to X12 are each independently C or N; the maximum number of N within a ring is two; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; RB and RC each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of RB, RC, R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form a ring; the ligand LA is complexed to a metal M through the two indicated dash lines of each Formula; and the ligand LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

CROSS-REFERENCE TO RELATED CASES

This application is a continuation of U.S. patent application Ser. No. 16/828,080, filed Mar. 24, 2020, which (i) claims priority under U.S.C. § 1.119(e) to U.S. Provisional application No. 62/930,837, filed on Nov. 5, 2019, and (ii) is a continuation-in-part of U.S. patent application Ser. No. 16/375,467, filed on Apr. 4, 2019, which is a continuation-in-part of U.S. patent application Ser. No. 15/950,351, filed on Apr. 11, 2018, which is a continuation-in-part of U.S. patent application Ser. No. 15/825,297, filed on Nov. 29, 2017, which is a continuation-in-part of co-pending U.S. patent application Ser. No. 15/706,186, filed on Sep. 15, 2017, that claims priority to U.S. Provisional application No. 62/403,424, filed Oct. 3, 2016, the disclosure of which is encorporated herein by reference.

FIELD

The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY

In one aspect, the present disclosure provides a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV:

where: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C, N, and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V

where indicated by “

”; X⁵ to X¹² are each independently C or N; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two substituents can be joined or fused to form a ring; the ligand L_(A) is complexed to a metal M through the two indicated dash lines of each Formula I, Formula II, Formula III, and Formula IV; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In another aspect, the present disclosure provides a formulation of a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV as described herein.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV as described herein.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 is a plot of photoluminescence (PL) spectra of the Inventive Example compound 1 and 2 and the Comparative Example compound 1 taken in 2-methylTHF solution at room temperature.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 maybe referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)—R_(S)).

The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R_(S) or —C(O)—O—R_(S)) radical.

The term “ether” refers to an —OR_(S) radical.

The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR_(S) radical.

The term “sulfinyl” refers to a —S(O)—R_(S) radical.

The term “sulfonyl” refers to a —SO₂—R_(S) radical.

The term “phosphino” refers to a —P(R_(S))₃ radical, wherein each R_(S) can be same or different.

The term “silyl” refers to a —Si(R_(S))₃ radical, wherein each R_(S) can be same or different.

The term “boryl” refers to a —B(R_(S))₂ radical or its Lewis adduct —B(R_(S))₃ radical, wherein R_(s) can be same or different.

In each of the above, R_(S) can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R_(s) is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.

The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group is optionally substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group is optionally substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group is optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group is optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group is optionally substituted.

The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group is optionally substituted.

Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.

In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R¹ represents mono-substitution, then one R¹ must be other than H (i.e., a substitution). Similarly, when R¹ represents di-substitution, then two of R¹ must be other than H. Similarly, when R¹ represents no substitution, R¹, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.

As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.

The Compounds of the Present Disclosure

In one aspect, the present disclosure provides a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV:

where: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C, N, and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula

where indicated by “

”; X⁵ to X¹² are each independently C or N; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two substituents can be joined or fused to form a ring; the ligand L_(A) is complexed to a metal M through the two indicated dash lines of each Formula I, Formula II, Formula III, and Formula IV; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments of the compound, the maximum number of N within a ring in the ligand L_(A) is two.

In some embodiments of the compound, each of R^(B), R^(C), R, R′, and R″ is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

In some embodiments of the compound, ring B is a 6-membered ring. In some embodiments where ring B is a 6-membered ring, each R is H.

In some embodiments of the compound, the ligand L_(A) is selected from the group consisting of the following structures:

wherein the relevant provisos for Formulas I and II apply to Formulas VI and VII.

In any of the embodiments of the compound mentioned above, each of X¹ to X⁴ is independently C or CR.

In some embodiments of the compound, at least one of X¹ to X⁴ in each formula is N.

In some embodiments of the compound, each of X⁵ to X⁸ is C.

In some embodiments of the compound, each of X⁹ to X¹² is C.

In some embodiments of the compound, each of X⁵ to X¹² is C.

In some embodiments of the compound, at least one of X⁵ to X¹² in each formula is N.

In some embodiments of the compound, at least one of X⁵ to X⁸ in each formula is N.

In some embodiments of the compound, at least one of X⁹ to X¹² in each formula is N.

In some embodiments of the compound, Z for each occurrence independently forms a direct bond to X¹. In some embodiments, Z for each occurrence independently forms a direct bond to X². In some embodiments, Z for each occurrence independently forms a direct bond to X³. In some embodiments, Z for each occurrence independently forms a direct bond to X⁴. In some embodiments, Z for each occurrence is independently O or S.

In some embodiments of the compound, each R^(C) in each of the Formulas I, II, III, and IV is H. In some embodiments, at least one R^(B) in each of the Formulas I, II, III, IV, VI, and VII is independently an alkyl or cycloalkyl group. In some embodiments, at least one R^(B) in each of the Formulas I, II, III, and IV is independently a tertiary alkyl group.

In some embodiments of the compound, Y for each occurrence is independently O or S.

In some embodiments of the compound, the ligand L_(A) is selected from the Ligand Group A consisting of the following structures:

In some embodiments of the compound, the compound comprises the ligand L_(A) selected from the Ligand Group B consisting of the following structures:

In some embodiments of the compound where the ligand L_(A) is selected from the Ligand Group A or the Ligand Group B, each of R^(B), R^(C), R, R′, and R″ for each Formula is independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

In some embodiments of the compound where the ligand L_(A) is selected from the Ligand Group B, the R^(B) substituent is para to the metal and is selected from the group consisting of alkyl, cycloalkyl, and combination thereof.

In some embodiments of the compound where the ligand L_(A) is selected from the Ligand Group B, the R^(B) substituent is para to the metal and is a tertiary alkyl. In some embodiments, the R^(B) substituent is para to the metal and is tert-butyl.

In some embodiments of the compound where the ligand L_(A) is selected from the Ligand Group A, X¹ to X⁴ for each formula in Ligand Group A are independently C or CR. In some embodiments, each R for each formula in Ligand Group A is independently H. In some embodiments, each of X⁵ to X⁸ for each formula in Ligand Group A is independently C. In some embodiments, each of X⁹ to X¹² for each formula in Ligand Group A is independently C. In some embodiments, each of X⁵ to X¹² for each formula in Ligand Group A is independently C. In some embodiments, at least one of X⁵ to X¹² for each formula in Ligand Group A is independently N. In some embodiments, at least one of X⁵ to X⁸ for each formula in Ligand Group A is independently N. In some embodiments, at least one of X⁹ to X¹² for each formula in Ligand Group A is independently N. In some embodiments, each R^(C) for each formula in Ligand Group A is independently H. In some embodiments, at least one R^(B) for each formula in Ligand Group A is independently an alkyl, cycloalkyl, or combination thereof. In some embodiments, at least one R^(B) for each formula in Ligand Group A is independently a tertiary alkyl group. In some embodiments, Z for each occurrence is independently O or S.

In some embodiments of the compound, the compound comprises a substituted or unsubstituted acetylacetonate ligand. In some embodiments of the compound, the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au. In some embodiments of the compound, the metal M is selected from the group consisting of Ir and Pt. In some embodiments of the compound, the compound comprises the ligand L_(A) selected from the group consisting of:

where each of R^(B) can be the same or different, each of R^(C) can be the same or different, and R^(B) and R^(C) for each occurrence is independently selected from the group consisting of the general substituents defined herein.

In some embodiments of the compound, the compound comprises the ligand L_(A) selected from the group consisting of

L_(Ai-1) based on Structure 1:

L_(Ai-2) based on Structure 2:

L_(Ai-3) based on Structure 3:

L_(Ai-4) G LAM based on Structure 4:

L_(Ai-5) based on Structure 5:

L_(Ai-6) based on Structure 6:

L_(Ai-7) based on Stracture 7:

L_(Ai-8) based on Structure 8:

L_(Ai-9) based on Structure 9:

L_(Ai-10) based on Structure 10:

L_(Ai-11) based on Structure 1:

L_(Ai-12) based on Structure 12:

L_(Ai-13) based on Structure 13:

L_(Ai-14) based on Structure 14:

L_(Ai-15) based on Structure 15:

L_(Ai-16) based on Structure 16:

L_(Ai-17) based on Structure 17:

L_(Ai-18) based on Structure 18:

L_(Ai-19) based on Structure 19:

L_(Ai-20) based on Structure 20:

L_(Ai-21) based on Structure 21:

L_(Ai-22) based on Structure 22:

L_(Ai-23) based on Structure 23:

L_(Ai-24) based on Structure 24:

L_(Ai-25) based on Structure 25:

L_(Ai-26) based on Structure 26:

L_(Ai-27) based on Structure 27:

L_(Ai-28) based on Structure 28:

L_(Ai-29) based on Structure 29:

L_(Ai-30) based on Structure 30:

L_(Ai-31) based on Structure 31:

L_(Ai-32) based on Structure 32:

L_(Ai-33) based on Structure 33:

L_(Ai-34) based on Structure 34:

L_(Ai-35) based on Structure 35:

wherein i is an integer from 1 to 1336, and for each i, R_(E), R_(F), and G are defined as below:

i R_(E) R_(F) G 1 R¹ R¹ G⁵ 2 R² R² G⁵ 3 R³ R³ G⁵ 4 R⁴ R⁴ G⁵ 5 R⁵ R⁵ G⁵ 6 R⁶ R⁶ G⁵ 7 R⁷ R⁷ G⁵ 8 R⁸ R⁸ G⁵ 9 R⁹ R⁹ G⁵ 10 R¹⁰ R¹⁰ G⁵ 11 R¹¹ R¹¹ G⁵ 12 R¹² R¹² G⁵ 13 R¹³ R¹³ G⁵ 14 R¹⁴ R¹⁴ G⁵ 15 R¹⁵ R¹⁵ G⁵ 16 R¹⁶ R¹⁶ G⁵ 17 R¹⁷ R¹⁷ G⁵ 18 R¹⁸ R¹⁸ G⁵ 19 R¹⁹ R¹⁹ G⁵ 20 R²⁰ R²⁰ G⁵ 21 R²¹ R²¹ G⁵ 22 R²² R²² G⁵ 23 R²³ R²³ G⁵ 24 R²⁴ R²⁴ G⁵ 25 R²⁵ R²⁵ G⁵ 26 R²⁶ R²⁶ G⁵ 27 R²⁷ R²⁷ G⁵ 28 R²⁸ R²⁸ G⁵ 29 R²⁹ R²⁹ G⁵ 30 R³⁰ R³⁰ G⁵ 31 R³¹ R³¹ G⁵ 32 R³² R³² G⁵ 31 R² R¹ G⁵ 32 R³ R¹ G⁵ 33 R⁴ R¹ G⁵ 34 R⁵ R¹ G⁵ 35 R⁶ R¹ G⁵ 36 R⁷ R¹ G⁵ 37 R⁸ R¹ G⁵ 38 R⁹ R¹ G⁵ 39 R¹⁰ R¹ G⁵ 40 R¹¹ R¹ G⁵ 41 R¹² R¹ G⁵ 42 R¹³ R¹ G⁵ 43 R¹⁴ R¹ G⁵ 44 R¹⁵ R¹ G⁵ 45 R¹⁶ R¹ G⁵ 46 R¹⁷ R¹ G⁵ 47 R¹⁸ R¹ G⁵ 48 R¹⁹ R¹ G⁵ 49 R²⁰ R¹ G⁵ 50 R²¹ R¹ G⁵ 51 R²² R¹ G⁵ 52 R²³ R¹ G⁵ 53 R²⁴ R¹ G⁵ 54 R²⁵ R¹ G⁵ 55 R²⁶ R¹ G⁵ 56 R²⁷ R¹ G⁵ 57 R²⁸ R¹ G⁵ 58 R²⁹ R¹ G⁵ 59 R³⁰ R¹ G⁵ 60 R³¹ R¹ G⁵ 61 R³² R¹ G⁵ 62 R¹ R² G⁵ 63 R¹ R³ G⁵ 64 R¹ R⁴ G⁵ 65 R¹ R⁵ G⁵ 66 R¹ R⁶ G⁵ 67 R¹ R⁷ G⁵ 68 R¹ R⁸ G⁵ 69 R¹ R⁹ G⁵ 70 R¹ R¹⁰ G⁵ 71 R¹ R¹¹ G⁵ 72 R¹ R¹² G⁵ 73 R¹ R¹³ G⁵ 74 R¹ R¹⁴ G⁵ 75 R¹ R¹⁵ G⁵ 76 R¹ R¹⁶ G⁵ 77 R¹ R¹⁷ G⁵ 78 R¹ R¹⁸ G⁵ 79 R¹ R¹⁹ G⁵ 80 R¹ R²⁰ G⁵ 81 R¹ R²¹ G⁵ 82 R¹ R²² G⁵ 83 R¹ R²³ G⁵ 84 R¹ R²⁴ G⁵ 85 R¹ R²⁵ G⁵ 86 R¹ R²⁶ G⁵ 87 R¹ R²⁷ G⁵ 88 R¹ R²⁸ G⁵ 89 R¹ R²⁹ G⁵ 90 R¹ R³⁰ G⁵ 91 R¹ R³¹ G⁵ 92 R¹ R³² G⁵ 93 R³ R² G⁵ 94 R⁴ R² G⁵ 95 R⁵ R² G⁵ 96 R⁶ R² G⁵ 97 R⁷ R² G⁵ 98 R⁸ R² G⁵ 99 R⁹ R² G⁵ 100 R¹⁰ R² G⁵ 101 R¹¹ R² G⁵ 102 R¹² R² G⁵ 103 R¹³ R² G⁵ 104 R¹⁴ R² G⁵ 105 R¹⁵ R² G⁵ 106 R¹⁶ R² G⁵ 107 R¹⁷ R² G⁵ 108 R¹⁸ R² G⁵ 109 R¹⁹ R² G⁵ 110 R²⁰ R² G⁵ 111 R²¹ R² G⁵ 112 R²² R² G⁵ 113 R²³ R² G⁵ 114 R²⁴ R² G⁵ 115 R²⁵ R² G⁵ 116 R²⁶ R² G⁵ 117 R²⁷ R² G⁵ 118 R²⁸ R² G⁵ 119 R²⁹ R² G⁵ 120 R³⁰ R² G⁵ 121 R³¹ R² G⁵ 122 R³² R² G⁵ 123 R² R³ G⁵ 124 R² R⁴ G⁵ 125 R² R⁵ G⁵ 126 R² R⁶ G⁵ 127 R² R⁷ G⁵ 128 R² R⁸ G⁵ 129 R² R⁹ G⁵ 130 R² R¹⁰ G⁵ 131 R² R¹¹ G⁵ 132 R² R¹² G⁵ 133 R² R¹³ G⁵ 134 R² R¹⁴ G⁵ 135 R² R¹⁵ G⁵ 136 R² R¹⁶ G⁵ 137 R² R¹⁷ G⁵ 138 R² R¹⁸ G⁵ 139 R² R¹⁹ G⁵ 140 R² R²⁰ G⁵ 141 R² R²¹ G⁵ 142 R² R²² G⁵ 143 R² R²³ G⁵ 144 R² R²⁴ G⁵ 145 R² R²⁵ G⁵ 146 R² R²⁶ G⁵ 147 R² R²⁷ G⁵ 148 R² R²⁸ G⁵ 149 R² R²⁹ G⁵ 150 R² R³⁰ G⁵ 151 R² R³¹ G⁵ 152 R² R³² G⁵ 153 R² R³² G⁵ 154 R³ R³² G⁵ 155 R⁴ R³² G⁵ 156 R⁵ R³² G⁵ 157 R⁶ R³² G⁵ 158 R⁷ R³² G⁵ 159 R⁸ R³² G⁵ 160 R⁹ R³² G⁵ 161 R¹⁰ R³² G⁵ 162 R¹¹ R³² G⁵ 163 R¹² R³² G⁵ 164 R¹³ R³² G⁵ 165 R¹⁴ R³² G⁵ 166 R¹⁵ R³² G⁵ 167 R¹⁶ R³² G⁵ 168 R¹⁷ R³² G⁵ 169 R¹⁸ R³² G⁵ 170 R¹⁹ R³² G⁵ 171 R²⁰ R³² G⁵ 172 R²¹ R³² G⁵ 173 R²² R³² G⁵ 174 R²³ R³² G⁵ 175 R²⁴ R³² G⁵ 176 R²⁵ R³² G⁵ 177 R²⁶ R³² G⁵ 178 R²⁷ R³² G⁵ 179 R²⁸ R³² G⁵ 180 R²⁹ R³² G⁵ 181 R³⁰ R³² G⁵ 182 R³¹ R³² G⁵ 183 R³² R² G⁵ 184 R³² R³ G⁵ 185 R³² R⁴ G⁵ 186 R³² R⁵ G⁵ 187 R³² R⁶ G⁵ 188 R³² R⁷ G⁵ 189 R³² R⁸ G⁵ 190 R³² R⁹ G⁵ 191 R³² R¹⁰ G⁵ 192 R³² R¹¹ G⁵ 193 R³² R¹² G⁵ 194 R³² R¹³ G⁵ 195 R³² R¹⁴ G⁵ 196 R³² R¹⁵ G⁵ 197 R³² R¹⁶ G⁵ 198 R³² R¹⁷ G⁵ 199 R³² R¹⁸ G⁵ 200 R³² R¹⁹ G⁵ 201 R³² R²⁰ G⁵ 202 R³² R²¹ G⁵ 203 R³² R²² G⁵ 204 R³² R²³ G⁵ 205 R³² R²⁴ G⁵ 206 R³² R²⁵ G⁵ 207 R³² R²⁶ G⁵ 208 R³² R²⁷ G⁵ 209 R³² R²⁸ G⁵ 210 R³² R²⁹ G⁵ 211 R³² R³⁰ G⁵ 212 R³² R³¹ G⁵ 213 R¹ R¹ G⁶ 214 R² R² G⁶ 215 R³ R³ G⁶ 216 R⁴ R⁴ G⁶ 217 R⁵ R⁵ G⁶ 218 R⁶ R⁶ G⁶ 219 R⁷ R⁷ G⁶ 220 R⁸ R⁸ G⁶ 221 R⁹ R⁹ G⁶ 222 R¹⁰ R¹⁰ G⁶ 223 R¹¹ R¹¹ G⁶ 224 R¹² R¹² G⁶ 225 R¹³ R¹³ G⁶ 226 R¹⁴ R¹⁴ G⁶ 227 R¹⁵ R¹⁵ G⁶ 228 R¹⁶ R¹⁶ G⁶ 229 R¹⁷ R¹⁷ G⁶ 230 R¹⁸ R¹⁸ G⁶ 231 R¹⁹ R¹⁹ G⁶ 232 R²⁰ R²⁰ G⁶ 233 R²¹ R²¹ G⁶ 234 R²² R²² G⁶ 235 R²³ R²³ G⁶ 236 R²⁴ R²⁴ G⁶ 237 R²⁵ R²⁵ G⁶ 238 R²⁶ R²⁶ G⁶ 239 R²⁷ R²⁷ G⁶ 240 R²⁸ R²⁸ G⁶ 241 R²⁹ R²⁹ G⁶ 242 R³⁰ R³⁰ G⁶ 243 R³¹ R³¹ G⁶ 244 R³² R³² G⁶ 245 R² R¹ G⁶ 246 R³ R¹ G⁶ 247 R⁴ R¹ G⁶ 248 R⁵ R¹ G⁶ 249 R⁶ R¹ G⁶ 250 R⁷ R¹ G⁶ 251 R⁸ R¹ G⁶ 252 R⁹ R¹ G⁶ 253 R¹⁰ R¹ G⁶ 254 R¹¹ R¹ G⁶ 255 R¹² R¹ G⁶ 256 R¹³ R¹ G⁶ 257 R¹⁴ R¹ G⁶ 258 R¹⁵ R¹ G⁶ 259 R¹⁶ R¹ G⁶ 260 R¹⁷ R¹ G⁶ 261 R¹⁸ R¹ G⁶ 262 R¹⁹ R¹ G⁶ 263 R²⁰ R¹ G⁶ 264 R²¹ R¹ G⁶ 265 R²² R¹ G⁶ 266 R²³ R¹ G⁶ 267 R²⁴ R¹ G⁶ 268 R²⁵ R¹ G⁶ 269 R²⁶ R¹ G⁶ 270 R²⁷ R¹ G⁶ 271 R²⁸ R¹ G⁶ 272 R²⁹ R¹ G⁶ 273 R³⁰ R¹ G⁶ 274 R³¹ R¹ G⁶ 275 R³² R¹ G⁶ 276 R¹ R² G⁶ 277 R¹ R³ G⁶ 278 R¹ R⁴ G⁶ 279 R¹ R⁵ G⁶ 280 R¹ R⁶ G⁶ 281 R¹ R⁷ G⁶ 282 R¹ R⁸ G⁶ 283 R¹ R⁹ G⁶ 284 R¹ R¹⁰ G⁶ 285 R¹ R¹¹ G⁶ 286 R¹ R¹² G⁶ 287 R¹ R¹³ G⁶ 288 R¹ R¹⁴ G⁶ 289 R¹ R¹⁵ G⁶ 290 R¹ R¹⁶ G⁶ 291 R¹ R¹⁷ G⁶ 292 R¹ R¹⁸ G⁶ 293 R¹ R¹⁹ G⁶ 294 R¹ R²⁰ G⁶ 295 R¹ R²¹ G⁶ 296 R¹ R²² G⁶ 297 R¹ R²³ G⁶ 298 R¹ R²⁴ G⁶ 299 R¹ R²⁵ G⁶ 300 R¹ R²⁶ G⁶ 301 R¹ R²⁷ G⁶ 302 R¹ R²⁸ G⁶ 303 R¹ R²⁹ G⁶ 304 R¹ R³⁰ G⁶ 305 R¹ R³¹ G⁶ 306 R¹ R³² G⁶ 307 R³ R² G⁶ 308 R⁴ R² G⁶ 309 R⁵ R² G⁶ 310 R⁶ R² G⁶ 311 R⁷ R² G⁶ 312 R⁸ R² G⁶ 313 R⁹ R² G⁶ 314 R¹⁰ R² G⁶ 315 R¹¹ R² G⁶ 316 R¹² R² G⁶ 317 R¹³ R² G⁶ 318 R¹⁴ R² G⁶ 319 R¹⁵ R² G⁶ 320 R¹⁶ R² G⁶ 321 R¹⁷ R² G⁶ 322 R¹⁸ R² G⁶ 323 R¹⁹ R² G⁶ 324 R²⁰ R² G⁶ 325 R²¹ R² G⁶ 326 R²² R² G⁶ 327 R²³ R² G⁶ 328 R²⁴ R² G⁶ 329 R²⁵ R² G⁶ 330 R²⁶ R² G⁶ 331 R²⁷ R² G⁶ 332 R²⁸ R² G⁶ 333 R²⁹ R² G⁶ 334 R³⁰ R² G⁶ 335 R³¹ R² G⁶ 336 R³² R² G⁶ 337 R² R³ G⁶ 338 R² R⁴ G⁶ 339 R² R⁵ G⁶ 340 R² R⁶ G⁶ 341 R² R⁷ G⁶ 342 R² R⁸ G⁶ 343 R² R⁹ G⁶ 344 R² R¹⁰ G⁶ 345 R² R¹¹ G⁶ 346 R² R¹² G⁶ 347 R² R¹³ G⁶ 348 R² R¹⁴ G⁶ 349 R² R¹⁵ G⁶ 350 R² R¹⁶ G⁶ 351 R² R¹⁷ G⁶ 352 R² R¹⁸ G⁶ 353 R² R¹⁹ G⁶ 354 R² R²⁰ G⁶ 355 R² R²¹ G⁶ 356 R² R²² G⁶ 357 R² R²³ G⁶ 358 R² R²⁴ G⁶ 359 R² R²⁵ G⁶ 360 R² R²⁶ G⁶ 361 R² R²⁷ G⁶ 362 R² R²⁸ G⁶ 363 R² R²⁹ G⁶ 364 R² R³⁰ G⁶ 365 R² R³¹ G⁶ 366 R² R³² G⁶ 367 R² R³² G⁶ 368 R³ R³² G⁶ 369 R⁴ R³² G⁶ 370 R⁵ R³² G⁶ 371 R⁶ R³² G⁶ 372 R⁷ R³² G⁶ 373 R⁸ R³² G⁶ 374 R⁹ R³² G⁶ 375 R¹⁰ R³² G⁶ 376 R¹¹ R³² G⁶ 377 R¹² R³² G⁶ 378 R¹³ R³² G⁶ 379 R¹⁴ R³² G⁶ 380 R¹⁵ R³² G⁶ 381 R¹⁶ R³² G⁶ 382 R¹⁷ R³² G⁶ 383 R¹⁸ R³² G⁶ 384 R¹⁹ R³² G⁶ 385 R²⁰ R³² G⁶ 386 R²¹ R³² G⁶ 387 R²² R³² G⁶ 388 R²³ R³² G⁶ 389 R²⁴ R³² G⁶ 390 R²⁵ R³² G⁶ 391 R²⁶ R³² G⁶ 392 R²⁷ R³² G⁶ 393 R²⁸ R³² G⁶ 394 R²⁹ R³² G⁶ 395 R³⁰ R³² G⁶ 396 R³¹ R³² G⁶ 397 R³² R² G⁶ 398 R³² R³ G⁶ 399 R³² R⁴ G⁶ 400 R³² R⁵ G⁶ 401 R³² R⁶ G⁶ 402 R³² R⁷ G⁶ 403 R³² R⁸ G⁶ 404 R³² R⁹ G⁶ 405 R³² R¹⁰ G⁶ 406 R³² R¹¹ G⁶ 407 R³² R¹² G⁶ 408 R³² R¹³ G⁶ 409 R³² R¹⁴ G⁶ 410 R³² R¹⁵ G⁶ 411 R³² R¹⁶ G⁶ 412 R³² R¹⁷ G⁶ 413 R³² R¹⁸ G⁶ 414 R³² R¹⁹ G⁶ 415 R³² R²⁰ G⁶ 416 R³² R²¹ G⁶ 417 R³² R²² G⁶ 418 R³² R²³ G⁶ 419 R³² R²⁴ G⁶ 420 R³² R²⁵ G⁶ 421 R³² R²⁶ G⁶ 422 R³² R²⁷ G⁶ 423 R³² R²⁸ G⁶ 424 R³² R²⁹ G⁶ 425 R³² R³⁰ G⁶ 426 R³² R³¹ G⁶ 427 R¹ R³³ G⁵ 428 R¹ R³⁴ G⁵ 429 R¹ R³⁵ G⁵ 430 R¹ R³⁶ G⁵ 431 R¹ R³⁷ G⁵ 432 R¹ R³⁸ G⁵ 433 R¹ R³⁹ G⁵ 434 R¹ R⁴⁰ G⁵ 435 R¹ R⁴¹ G⁵ 436 R³³ R¹ G⁵ 437 R³⁴ R¹ G⁵ 438 R³⁵ R¹ G⁵ 439 R³⁶ R¹ G⁵ 440 R³⁷ R¹ G⁵ 441 R³⁸ R¹ G⁵ 442 R³⁹ R¹ G⁵ 443 R⁴⁰ R¹ G⁵ 444 R⁴¹ R¹ G⁵ 445 R¹ R¹ G⁸ 446 R² R² G⁸ 447 R³ R³ G⁸ 448 R⁴ R⁴ G⁸ 449 R⁵ R⁵ G⁸ 450 R⁶ R⁶ G⁸ 451 R⁷ R⁷ G⁸ 452 R⁸ R⁸ G⁸ 453 R⁹ R⁹ G⁸ 454 R¹⁰ R¹⁰ G⁸ 455 R¹¹ R¹¹ G⁸ 456 R¹² R¹² G⁸ 457 R¹³ R¹³ G⁸ 458 R¹⁴ R¹⁴ G⁸ 459 R¹⁵ R¹⁵ G⁸ 460 R¹⁶ R¹⁶ G⁸ 461 R¹⁷ R¹⁷ G⁸ 462 R¹⁸ R¹⁸ G⁸ 463 R¹⁹ R¹⁹ G⁸ 464 R²⁰ R²⁰ G⁸ 465 R²¹ R²¹ G⁸ 466 R²² R²² G⁸ 467 R²³ R²³ G⁸ 468 R²⁴ R²⁴ G⁸ 469 R²⁵ R²⁵ G⁸ 470 R²⁶ R²⁶ G⁸ 471 R²⁷ R²⁷ G⁸ 472 R²⁸ R²⁸ G⁸ 473 R²⁹ R²⁹ G⁸ 474 R³⁰ R³⁰ G⁸ 475 R³¹ R³¹ G⁸ 476 R³² R³² G⁸ 477 R² R¹ G⁸ 478 R³ R¹ G⁸ 479 R⁴ R¹ G⁸ 480 R⁵ R¹ G⁸ 481 R⁶ R¹ G⁸ 482 R⁷ R¹ G⁸ 483 R⁸ R¹ G⁸ 484 R⁹ R¹ G⁸ 485 R¹⁰ R¹ G⁸ 486 R¹¹ R¹ G⁸ 487 R¹² R¹ G⁸ 488 R¹³ R¹ G⁸ 489 R¹⁴ R¹ G⁸ 490 R¹⁵ R¹ G⁸ 491 R¹⁶ R¹ G⁸ 492 R¹⁷ R¹ G⁸ 493 R¹⁸ R¹ G⁸ 494 R¹⁹ R¹ G⁸ 495 R²⁰ R¹ G⁸ 496 R²¹ R¹ G⁸ 497 R²² R¹ G⁸ 498 R²³ R¹ G⁸ 499 R²⁴ R¹ G⁸ 500 R²⁵ R¹ G⁸ 501 R²⁶ R¹ G⁸ 502 R²⁷ R¹ G⁸ 503 R²⁸ R¹ G⁸ 504 R²⁹ R¹ G⁸ 505 R³⁰ R¹ G⁸ 506 R³¹ R¹ G⁸ 507 R³² R¹ G⁸ 508 R¹ R² G⁸ 509 R¹ R³ G⁸ 510 R¹ R⁴ G⁸ 511 R¹ R⁵ G⁸ 512 R¹ R⁶ G⁸ 513 R¹ R⁷ G⁸ 514 R¹ R⁸ G⁸ 515 R¹ R⁹ G⁸ 516 R¹ R¹⁰ G⁸ 517 R¹ R¹¹ G⁸ 518 R¹ R¹² G⁸ 519 R¹ R¹³ G⁸ 520 R¹ R¹⁴ G⁸ 521 R¹ R¹⁵ G⁸ 522 R¹ R¹⁶ G⁸ 523 R¹ R¹⁷ G⁸ 524 R¹ R¹⁸ G⁸ 525 R¹ R¹⁹ G⁸ 526 R¹ R²⁰ G⁸ 527 R¹ R²¹ G⁸ 528 R¹ R²² G⁸ 529 R¹ R²³ G⁸ 530 R¹ R²⁴ G⁸ 531 R¹ R²⁵ G⁸ 532 R¹ R²⁶ G⁸ 533 R¹ R²⁷ G⁸ 534 R¹ R²⁸ G⁸ 535 R¹ R²⁹ G⁸ 536 R¹ R³⁰ G⁸ 537 R¹ R³¹ G⁸ 538 R¹ R³² G⁸ 539 R³ R² G⁸ 540 R⁴ R² G⁸ 541 R⁵ R² G⁸ 542 R⁶ R² G⁸ 543 R⁷ R² G⁸ 544 R⁸ R² G⁸ 545 R⁹ R² G⁸ 546 R¹⁰ R² G⁸ 547 R¹¹ R² G⁸ 548 R¹² R² G⁸ 549 R¹³ R² G⁸ 550 R¹⁴ R² G⁸ 551 R¹⁵ R² G⁸ 552 R¹⁶ R² G⁸ 553 R¹⁷ R² G⁸ 554 R¹⁸ R² G⁸ 555 R¹⁹ R² G⁸ 556 R²⁰ R² G⁸ 557 R²¹ R² G⁸ 558 R²² R² G⁸ 559 R²³ R² G⁸ 560 R²⁴ R² G⁸ 561 R²⁵ R² G⁸ 562 R²⁶ R² G⁸ 563 R²⁷ R² G⁸ 564 R²⁸ R² G⁸ 565 R²⁹ R² G⁸ 566 R³⁰ R² G⁸ 567 R³¹ R² G⁸ 568 R³² R² G⁸ 569 R² R³ G⁸ 570 R² R⁴ G⁸ 571 R² R⁵ G⁸ 572 R² R⁶ G⁸ 573 R² R⁷ G⁸ 574 R² R⁸ G⁸ 575 R² R⁹ G⁸ 576 R² R¹⁰ G⁸ 577 R² R¹¹ G⁸ 578 R² R¹² G⁸ 579 R² R¹³ G⁸ 580 R² R¹⁴ G⁸ 581 R² R¹⁵ G⁸ 582 R² R¹⁶ G⁸ 583 R² R¹⁷ G⁸ 584 R² R¹⁸ G⁸ 585 R² R¹⁹ G⁸ 586 R² R²⁰ G⁸ 587 R² R²¹ G⁸ 588 R² R²² G⁸ 589 R² R²³ G⁸ 590 R² R²⁴ G⁸ 591 R² R²⁵ G⁸ 592 R² R²⁶ G⁸ 593 R² R²⁷ G⁸ 594 R² R²⁸ G⁸ 595 R² R²⁹ G⁸ 596 R² R³⁰ G⁸ 597 R² R³¹ G⁸ 598 R² R³² G⁸ 599 R² R³² G⁸ 600 R³ R³² G⁸ 601 R⁴ R³² G⁸ 602 R⁵ R³² G⁸ 603 R⁶ R³² G⁸ 604 R⁷ R³² G⁸ 605 R⁸ R³² G⁸ 606 R⁹ R³² G⁸ 607 R¹⁰ R³² G⁸ 608 R¹¹ R³² G⁸ 609 R¹² R³² G⁸ 610 R¹³ R³² G⁸ 611 R¹⁴ R³² G⁸ 612 R¹⁵ R³² G⁸ 613 R¹⁶ R³² G⁸ 614 R¹⁷ R³² G⁸ 615 R¹⁸ R³² G⁸ 616 R¹⁹ R³² G⁸ 617 R²⁰ R³² G⁸ 618 R²¹ R³² G⁸ 619 R²² R³² G⁸ 620 R²³ R³² G⁸ 621 R²⁴ R³² G⁸ 622 R²⁵ R³² G⁸ 623 R²⁶ R³² G⁸ 624 R²⁷ R³² G⁸ 625 R²⁸ R³² G⁸ 626 R²⁹ R³² G⁸ 627 R³⁰ R³² G⁸ 628 R³¹ R³² G⁸ 629 R³² R² G⁸ 630 R³² R³ G⁸ 631 R³² R⁴ G⁸ 632 R³² R⁵ G⁸ 633 R³² R⁶ G⁸ 634 R³² R⁷ G⁸ 635 R³² R⁸ G⁸ 636 R³² R⁹ G⁸ 637 R³² R¹⁰ G⁸ 638 R³² R¹¹ G⁸ 639 R³² R¹² G⁸ 640 R³² R¹³ G⁸ 641 R³² R¹⁴ G⁸ 642 R³² R¹⁵ G⁸ 643 R³² R¹⁶ G⁸ 644 R³² R¹⁷ G⁸ 645 R³² R¹⁸ G⁸ 646 R³² R¹⁹ G⁸ 647 R³² R²⁰ G⁸ 648 R³² R²¹ G⁸ 649 R³² R²² G⁸ 650 R³² R²³ G⁸ 651 R³² R²⁴ G⁸ 652 R³² R²⁵ G⁸ 653 R³² R²⁶ G⁸ 654 R³² R²⁷ G⁸ 655 R³² R²⁸ G⁸ 656 R³² R²⁹ G⁸ 657 R³² R³⁰ G⁸ 658 R³² R³¹ G⁸ 659 R¹ R¹ G⁹ 660 R² R² G⁹ 661 R³ R³ G⁹ 662 R⁴ R⁴ G⁹ 663 R⁵ R⁵ G⁹ 664 R⁶ R⁶ G⁹ 665 R⁷ R⁷ G⁹ 666 R⁸ R⁸ G⁹ 667 R⁹ R⁹ G⁹ 668 R¹⁰ R¹⁰ G⁹ 669 R¹¹ R¹¹ G⁹ 670 R¹² R¹² G⁹ 671 R¹³ R¹³ G⁹ 672 R¹⁴ R¹⁴ G⁹ 673 R¹⁵ R¹⁵ G⁹ 674 R¹⁶ R¹⁶ G⁹ 675 R¹⁷ R¹⁷ G⁹ 676 R¹⁸ R¹⁸ G⁹ 677 R¹⁹ R¹⁹ G⁹ 678 R²⁰ R²⁰ G⁹ 679 R²¹ R²¹ G⁹ 680 R²² R²² G⁹ 681 R²³ R²³ G⁹ 682 R²⁴ R²⁴ G⁹ 683 R²⁵ R²⁵ G⁹ 684 R²⁶ R²⁶ G⁹ 685 R²⁷ R²⁷ G⁹ 686 R²⁸ R²⁸ G⁹ 687 R²⁹ R²⁹ G⁹ 688 R³⁰ R³⁰ G⁹ 689 R³¹ R³¹ G⁹ 690 R³² R³² G⁹ 691 R² R¹ G⁹ 692 R³ R¹ G⁹ 693 R⁴ R¹ G⁹ 694 R⁵ R¹ G⁹ 695 R⁶ R¹ G⁹ 696 R⁷ R¹ G⁹ 697 R⁸ R¹ G⁹ 698 R⁹ R¹ G⁹ 699 R¹⁰ R¹ G⁹ 700 R¹¹ R¹ G⁹ 701 R¹² R¹ G⁹ 702 R¹³ R¹ G⁹ 703 R¹⁴ R¹ G⁹ 704 R¹⁵ R¹ G⁹ 705 R¹⁶ R¹ G⁹ 706 R¹⁷ R¹ G⁹ 707 R¹⁸ R¹ G⁹ 708 R¹⁹ R¹ G⁹ 709 R²⁰ R¹ G⁹ 710 R²¹ R¹ G⁹ 711 R²² R¹ G⁹ 712 R²³ R¹ G⁹ 713 R²⁴ R¹ G⁹ 714 R²⁵ R¹ G⁹ 715 R²⁶ R¹ G⁹ 716 R²⁷ R¹ G⁹ 717 R²⁸ R¹ G⁹ 718 R²⁹ R¹ G⁹ 719 R³⁰ R¹ G⁹ 720 R³¹ R¹ G⁹ 721 R³² R¹ G⁹ 722 R¹ R² G⁹ 723 R¹ R³ G⁹ 724 R¹ R⁴ G⁹ 725 R¹ R⁵ G⁹ 726 R¹ R⁶ G⁹ 727 R¹ R⁷ G⁹ 728 R¹ R⁸ G⁹ 729 R¹ R⁹ G⁹ 730 R¹ R¹⁰ G⁹ 731 R¹ R¹¹ G⁹ 732 R¹ R¹² G⁹ 733 R¹ R¹³ G⁹ 734 R¹ R¹⁴ G⁹ 735 R¹ R¹⁵ G⁹ 736 R¹ R¹⁶ G⁹ 737 R¹ R¹⁷ G⁹ 738 R¹ R¹⁸ G⁹ 739 R¹ R¹⁹ G⁹ 740 R¹ R²⁰ G⁹ 741 R¹ R²¹ G⁹ 742 R¹ R²² G⁹ 743 R¹ R²³ G⁹ 744 R¹ R²⁴ G⁹ 745 R¹ R²⁵ G⁹ 746 R¹ R²⁶ G⁹ 747 R¹ R²⁷ G⁹ 748 R¹ R²⁸ G⁹ 749 R¹ R²⁹ G⁹ 750 R¹ R³⁰ G⁹ 751 R¹ R³¹ G⁹ 752 R¹ R³² G⁹ 753 R³ R² G⁹ 754 R⁴ R² G⁹ 755 R⁵ R² G⁹ 756 R⁶ R² G⁹ 757 R⁷ R² G⁹ 758 R⁸ R² G⁹ 759 R⁹ R² G⁹ 760 R¹⁰ R² G⁹ 761 R¹¹ R² G⁹ 762 R¹² R² G⁹ 763 R¹³ R² G⁹ 764 R¹⁴ R² G⁹ 765 R¹⁵ R² G⁹ 766 R¹⁶ R² G⁹ 767 R¹⁷ R² G⁹ 768 R¹⁸ R² G⁹ 769 R¹⁹ R² G⁹ 770 R²⁰ R² G⁹ 771 R²¹ R² G⁹ 772 R²² R² G⁹ 773 R²³ R² G⁹ 774 R²⁴ R² G⁹ 775 R²⁵ R² G⁹ 776 R²⁶ R² G⁹ 777 R²⁷ R² G⁹ 778 R²⁸ R² G⁹ 779 R²⁹ R² G⁹ 780 R³⁰ R² G⁹ 781 R³¹ R² G⁹ 782 R³² R² G⁹ 783 R² R³ G⁹ 784 R² R⁴ G⁹ 785 R² R⁵ G⁹ 786 R² R⁶ G⁹ 787 R² R⁷ G⁹ 788 R² R⁸ G⁹ 789 R² R⁹ G⁹ 790 R² R¹⁰ G⁹ 791 R² R¹¹ G⁹ 792 R² R¹² G⁹ 793 R² R¹³ G⁹ 794 R² R¹⁴ G⁹ 795 R² R¹⁵ G⁹ 796 R² R¹⁶ G⁹ 797 R² R¹⁷ G⁹ 798 R² R¹⁸ G⁹ 799 R² R¹⁹ G⁹ 800 R² R²⁰ G⁹ 801 R² R²¹ G⁹ 802 R² R²² G⁹ 803 R² R²³ G⁹ 804 R² R²⁴ G⁹ 805 R² R²⁵ G⁹ 806 R² R²⁶ G⁹ 807 R² R²⁷ G⁹ 808 R² R²⁸ G⁹ 809 R² R²⁹ G⁹ 810 R² R³⁰ G⁹ 811 R² R³¹ G⁹ 812 R² R³² G⁹ 813 R² R³² G⁹ 814 R³ R³² G⁹ 815 R⁴ R³² G⁹ 816 R⁵ R³² G⁹ 817 R⁶ R³² G⁹ 818 R⁷ R³² G⁹ 819 R⁸ R³² G⁹ 820 R⁹ R³² G⁹ 821 R¹⁰ R³² G⁹ 822 R¹¹ R³² G⁹ 823 R¹² R³² G⁹ 824 R¹³ R³² G⁹ 825 R¹⁴ R³² G⁹ 826 R¹⁵ R³² G⁹ 827 R¹⁶ R³² G⁹ 828 R¹⁷ R³² G⁹ 829 R¹⁸ R³² G⁹ 830 R¹⁹ R³² G⁹ 831 R²⁰ R³² G⁹ 832 R²¹ R³² G⁹ 833 R²² R³² G⁹ 834 R²³ R³² G⁹ 835 R²⁴ R³² G⁹ 836 R²⁵ R³² G⁹ 837 R²⁶ R³² G⁹ 838 R²⁷ R³² G⁹ 839 R²⁸ R³² G⁹ 840 R²⁹ R³² G⁹ 841 R³⁰ R³² G⁹ 842 R³¹ R³² G⁹ 843 R³² R² G⁹ 844 R³² R³ G⁹ 845 R³² R⁴ G⁹ 846 R³² R⁵ G⁹ 847 R³² R⁶ G⁹ 848 R³² R⁷ G⁹ 849 R³² R⁸ G⁹ 850 R³² R⁹ G⁹ 851 R³² R¹⁰ G⁹ 852 R³² R¹¹ G⁹ 853 R³² R¹² G⁹ 854 R³² R¹³ G⁹ 855 R³² R¹⁴ G⁹ 856 R³² R¹⁵ G⁹ 857 R³² R¹⁶ G⁹ 858 R³² R¹⁷ G⁹ 859 R³² R¹⁸ G⁹ 860 R³² R¹⁹ G⁹ 861 R³² R²⁰ G⁹ 862 R³² R²¹ G⁹ 863 R³² R²² G⁹ 864 R³² R²³ G⁹ 865 R³² R²⁴ G⁹ 866 R³² R²⁵ G⁹ 867 R³² R²⁶ G⁹ 868 R³² R²⁷ G⁹ 869 R³² R²⁸ G⁹ 870 R³² R²⁹ G⁹ 871 R³² R³⁰ G⁹ 872 R³² R³¹ G⁹ 873 R¹ R³³ G¹¹ 874 R¹ R³⁴ G¹¹ 875 R¹ R³⁵ G¹¹ 876 R¹ R³⁶ G¹¹ 877 R¹ R³⁷ G¹¹ 878 R¹ R³⁸ G¹¹ 879 R¹ R³⁹ G¹¹ 880 R¹ R⁴⁰ G¹¹ 881 R¹ R⁴¹ G¹¹ 882 R³³ R¹ G¹¹ 883 R³⁴ R¹ G¹¹ 884 R³⁵ R¹ G¹¹ 885 R³⁶ R¹ G¹¹ 886 R³⁷ R¹ G¹¹ 887 R³⁸ R¹ G¹¹ 888 R³⁹ R¹ G¹¹ 889 R⁴⁰ R¹ G¹¹ 890 R⁴¹ R¹ G¹¹ 891 R¹ R¹ G¹¹ 892 R² R² G¹¹ 893 R³ R³ G¹¹ 894 R⁴ R⁴ G¹¹ 895 R⁵ R⁵ G¹¹ 896 R⁶ R⁶ G¹¹ 897 R⁷ R⁷ G¹¹ 898 R⁸ R⁸ G¹¹ 899 R⁹ R⁹ G¹¹ 900 R¹⁰ R¹⁰ G¹¹ 901 R¹¹ R¹¹ G¹¹ 902 R¹² R¹² G¹¹ 903 R¹³ R¹³ G¹¹ 904 R¹⁴ R¹⁴ G¹¹ 905 R¹⁵ R¹⁵ G¹¹ 906 R¹⁶ R¹⁶ G¹¹ 907 R¹⁷ R¹⁷ G¹¹ 908 R¹⁸ R¹⁸ G¹¹ 909 R¹⁹ R¹⁹ G¹¹ 910 R²⁰ R²⁰ G¹¹ 911 R²¹ R²¹ G¹¹ 912 R²² R²² G¹¹ 913 R²³ R²³ G¹¹ 914 R²⁴ R²⁴ G¹¹ 915 R²⁵ R²⁵ G¹¹ 916 R²⁶ R²⁶ G¹¹ 917 R²⁷ R²⁷ G¹¹ 918 R²⁸ R²⁸ G¹¹ 919 R²⁹ R²⁹ G¹¹ 920 R³⁰ R³⁰ G¹¹ 921 R³¹ R³¹ G¹¹ 922 R³² R³² G¹¹ 923 R² R¹ G¹¹ 924 R³ R¹ G¹¹ 925 R⁴ R¹ G¹¹ 926 R⁵ R¹ G¹¹ 927 R⁶ R¹ G¹¹ 928 R⁷ R¹ G¹¹ 929 R⁸ R¹ G¹¹ 930 R⁹ R¹ G¹¹ 931 R¹⁰ R¹ G¹¹ 932 R¹¹ R¹ G¹¹ 933 R¹² R¹ G¹¹ 934 R¹³ R¹ G¹¹ 935 R¹⁴ R¹ G¹¹ 936 R¹⁵ R¹ G¹¹ 937 R¹⁶ R¹ G¹¹ 938 R¹⁷ R¹ G¹¹ 939 R¹⁸ R¹ G¹¹ 940 R¹⁹ R¹ G¹¹ 941 R²⁰ R¹ G¹¹ 942 R²¹ R¹ G¹¹ 943 R²² R¹ G¹¹ 944 R²³ R¹ G¹¹ 945 R²⁴ R¹ G¹¹ 946 R²⁵ R¹ G¹¹ 947 R²⁶ R¹ G¹¹ 948 R²⁷ R¹ G¹¹ 949 R²⁸ R¹ G¹¹ 950 R²⁹ R¹ G¹¹ 951 R³⁰ R¹ G¹¹ 952 R³¹ R¹ G¹¹ 953 R³² R¹ G¹¹ 954 R¹ R² G¹¹ 955 R¹ R³ G¹¹ 956 R¹ R⁴ G¹¹ 957 R¹ R⁵ G¹¹ 958 R¹ R⁶ G¹¹ 959 R¹ R⁷ G¹¹ 960 R¹ R⁸ G¹¹ 961 R¹ R⁹ G¹¹ 962 R¹ R¹⁰ G¹¹ 963 R¹ R¹¹ G¹¹ 964 R¹ R¹² G¹¹ 965 R¹ R¹³ G¹¹ 966 R¹ R¹⁴ G¹¹ 967 R¹ R¹⁵ G¹¹ 968 R¹ R¹⁶ G¹¹ 969 R¹ R¹⁷ G¹¹ 970 R¹ R¹⁸ G¹¹ 971 R¹ R¹⁹ G¹¹ 972 R¹ R²⁰ G¹¹ 973 R¹ R²¹ G¹¹ 974 R¹ R²² G¹¹ 975 R¹ R²³ G¹¹ 976 R¹ R²⁴ G¹¹ 977 R¹ R²⁵ G¹¹ 978 R¹ R²⁶ G¹¹ 979 R¹ R²⁷ G¹¹ 980 R¹ R²⁸ G¹¹ 981 R¹ R²⁹ G¹¹ 982 R¹ R³⁰ G¹¹ 983 R¹ R³¹ G¹¹ 984 R¹ R³² G¹¹ 985 R³ R² G¹¹ 986 R⁴ R² G¹¹ 987 R⁵ R² G¹¹ 988 R⁶ R² G¹¹ 989 R⁷ R² G¹¹ 990 R⁸ R² G¹¹ 991 R⁹ R² G¹¹ 992 R¹⁰ R² G¹¹ 993 R¹¹ R² G¹¹ 994 R¹² R² G¹¹ 995 R¹³ R² G¹¹ 996 R¹⁴ R² G¹¹ 997 R¹⁵ R² G¹¹ 998 R¹⁶ R² G¹¹ 999 R¹⁷ R² G¹¹ 1000 R¹⁸ R² G¹¹ 1001 R¹⁹ R² G¹¹ 1002 R²⁰ R² G¹¹ 1003 R²¹ R² G¹¹ 1004 R²² R² G¹¹ 1005 R²³ R² G¹¹ 1006 R²⁴ R² G¹¹ 1007 R²⁵ R² G¹¹ 1008 R²⁶ R² G¹¹ 1009 R²⁷ R² G¹¹ 1010 R²⁸ R² G¹¹ 1011 R²⁹ R² G¹¹ 1012 R³⁰ R² G¹¹ 1013 R³¹ R² G¹¹ 1014 R³² R² G¹¹ 1015 R² R³ G¹¹ 1016 R² R⁴ G¹¹ 1017 R² R⁵ G¹¹ 1018 R² R⁶ G¹¹ 1019 R² R⁷ G¹¹ 1020 R² R⁸ G¹¹ 1021 R² R⁹ G¹¹ 1022 R² R¹⁰ G¹¹ 1023 R² R¹¹ G¹¹ 1024 R² R¹² G¹¹ 1025 R² R¹³ G¹¹ 1026 R² R¹⁴ G¹¹ 1027 R² R¹⁵ G¹¹ 1028 R² R¹⁶ G¹¹ 1029 R² R¹⁷ G¹¹ 1030 R² R¹⁸ G¹¹ 1031 R² R¹⁹ G¹¹ 1032 R² R²⁰ G¹¹ 1033 R² R²¹ G¹¹ 1034 R² R²² G¹¹ 1035 R² R²³ G¹¹ 1036 R² R²⁴ G¹¹ 1037 R² R²⁵ G¹¹ 1038 R² R²⁶ G¹¹ 1039 R² R²⁷ G¹¹ 1040 R² R²⁸ G¹¹ 1041 R² R²⁹ G¹¹ 1042 R² R³⁰ G¹¹ 1043 R² R³¹ G¹¹ 1044 R² R³² G¹¹ 1045 R² R³² G¹¹ 1046 R³ R³² G¹¹ 1047 R⁴ R³² G¹¹ 1048 R⁵ R³² G¹¹ 1049 R⁶ R³² G¹¹ 1050 R⁷ R³² G¹¹ 1051 R⁸ R³² G¹¹ 1052 R⁹ R³² G¹¹ 1053 R¹⁰ R³² G¹¹ 1054 R¹¹ R³² G¹¹ 1055 R¹² R³² G¹¹ 1056 R¹³ R³² G¹¹ 1057 R¹⁴ R³² G¹¹ 1058 R¹⁵ R³² G¹¹ 1059 R¹⁶ R³² G¹¹ 1060 R¹⁷ R³² G¹¹ 1061 R¹⁸ R³² G¹¹ 1062 R¹⁹ R³² G¹¹ 1063 R²⁰ R³² G¹¹ 1064 R²¹ R³² G¹¹ 1065 R²² R³² G¹¹ 1066 R²³ R³² G¹¹ 1067 R²⁴ R³² G¹¹ 1068 R²⁵ R³² G¹¹ 1069 R²⁶ R³² G¹¹ 1070 R²⁷ R³² G¹¹ 1071 R²⁸ R³² G¹¹ 1072 R²⁹ R³² G¹¹ 1073 R³⁰ R³² G¹¹ 1074 R³¹ R³² G¹¹ 1075 R³² R² G¹¹ 1076 R³² R³ G¹¹ 1077 R³² R⁴ G¹¹ 1078 R³² R⁵ G¹¹ 1079 R³² R⁶ G¹¹ 1080 R³² R⁷ G¹¹ 1081 R³² R⁸ G¹¹ 1082 R³² R⁹ G¹¹ 1083 R³² R¹⁰ G¹¹ 1084 R³² R¹¹ G¹¹ 1085 R³² R¹² G¹¹ 1086 R³² R¹³ G¹¹ 1087 R³² R¹⁴ G¹¹ 1088 R³² R¹⁵ G¹¹ 1089 R³² R¹⁶ G¹¹ 1090 R³² R¹⁷ G¹¹ 1091 R³² R¹⁸ G¹¹ 1092 R³² R¹⁹ G¹¹ 1093 R³² R²⁰ G¹¹ 1094 R³² R²¹ G¹¹ 1095 R³² R²² G¹¹ 1096 R³² R²³ G¹¹ 1097 R³² R²⁴ G¹¹ 1098 R³² R²⁵ G¹¹ 1099 R³² R²⁶ G¹¹ 1100 R³² R²⁷ G¹¹ 1101 R³² R²⁸ G¹¹ 1102 R³² R²⁹ G¹¹ 1103 R³² R³⁰ G¹¹ 1104 R³² R³¹ G¹¹ 1105 R¹ R¹ G¹³ 1106 R² R² G¹³ 1107 R³ R³ G¹³ 1108 R⁴ R⁴ G¹³ 1109 R⁵ R⁵ G¹³ 1110 R⁶ R⁶ G¹³ 1111 R⁷ R⁷ G¹³ 1112 R⁸ R⁸ G¹³ 1113 R⁹ R⁹ G¹³ 1114 R¹⁰ R¹⁰ G¹³ 1115 R¹¹ R¹¹ G¹³ 1116 R¹² R¹² G¹³ 1117 R¹³ R¹³ G¹³ 1118 R¹⁴ R¹⁴ G¹³ 1119 R¹⁵ R¹⁵ G¹³ 1120 R¹⁶ R¹⁶ G¹³ 1121 R¹⁷ R¹⁷ G¹³ 1122 R¹⁸ R¹⁸ G¹³ 1123 R¹⁹ R¹⁹ G¹³ 1124 R²⁰ R²⁰ G¹³ 1125 R²¹ R²¹ G¹³ 1126 R²² R²² G¹³ 1127 R²³ R²³ G¹³ 1128 R²⁴ R²⁴ G¹³ 1129 R²⁵ R²⁵ G¹³ 1130 R²⁶ R²⁶ G¹³ 1131 R²⁷ R²⁷ G¹³ 1132 R²⁸ R²⁸ G¹³ 1133 R²⁹ R²⁹ G¹³ 1134 R³⁰ R³⁰ G¹³ 1135 R³¹ R³¹ G¹³ 1136 R³² R³² G¹³ 1137 R² R¹ G¹³ 1138 R³ R¹ G¹³ 1139 R⁴ R¹ G¹³ 1140 R⁵ R¹ G¹³ 1141 R⁶ R¹ G¹³ 1142 R⁷ R¹ G¹³ 1143 R⁸ R¹ G¹³ 1144 R⁹ R¹ G¹³ 1145 R¹⁰ R¹ G¹³ 1146 R¹¹ R¹ G¹³ 1147 R¹² R¹ G¹³ 1148 R¹³ R¹ G¹³ 1149 R¹⁴ R¹ G¹³ 1150 R¹⁵ R¹ G¹³ 1151 R¹⁶ R¹ G¹³ 1152 R¹⁷ R¹ G¹³ 1153 R¹⁸ R¹ G¹³ 1154 R¹⁹ R¹ G¹³ 1155 R²⁰ R¹ G¹³ 1156 R²¹ R¹ G¹³ 1157 R²² R¹ G¹³ 1158 R²³ R¹ G¹³ 1159 R²⁴ R¹ G¹³ 1160 R²⁵ R¹ G¹³ 1161 R²⁶ R¹ G¹³ 1162 R²⁷ R¹ G¹³ 1163 R²⁸ R¹ G¹³ 1164 R²⁹ R¹ G¹³ 1165 R³⁰ R¹ G¹³ 1166 R³¹ R¹ G¹³ 1167 R³² R¹ G¹³ 1168 R¹ R² G¹³ 1169 R¹ R³ G¹³ 1170 R¹ R⁴ G¹³ 1171 R¹ R⁵ G¹³ 1172 R¹ R⁶ G¹³ 1173 R¹ R⁷ G¹³ 1174 R¹ R⁸ G¹³ 1175 R¹ R⁹ G¹³ 1176 R¹ R¹⁰ G¹³ 1177 R¹ R¹¹ G¹³ 1178 R¹ R¹² G¹³ 1179 R¹ R¹³ G¹³ 1180 R¹ R¹⁴ G¹³ 1181 R¹ R¹⁵ G¹³ 1182 R¹ R¹⁶ G¹³ 1183 R¹ R¹⁷ G¹³ 1184 R¹ R¹⁸ G¹³ 1185 R¹ R¹⁹ G¹³ 1186 R¹ R²⁰ G¹³ 1187 R¹ R²¹ G¹³ 1188 R¹ R²² G¹³ 1189 R¹ R²³ G¹³ 1190 R¹ R²⁴ G¹³ 1191 R¹ R²⁵ G¹³ 1192 R¹ R²⁶ G¹³ 1193 R¹ R²⁷ G¹³ 1194 R¹ R²⁸ G¹³ 1195 R¹ R²⁹ G¹³ 1196 R¹ R³⁰ G¹³ 1197 R¹ R³¹ G¹³ 1198 R¹ R³² G¹³ 1199 R³ R² G¹³ 1200 R⁴ R² G¹³ 1201 R⁵ R² G¹³ 1202 R⁶ R² G¹³ 1203 R⁷ R² G¹³ 1204 R⁸ R² G¹³ 1205 R⁹ R² G¹³ 1206 R¹⁰ R² G¹³ 1207 R¹¹ R² G¹³ 1208 R¹² R² G¹³ 1209 R¹³ R² G¹³ 1210 R¹⁴ R² G¹³ 1211 R¹⁵ R² G¹³ 1212 R¹⁶ R² G¹³ 1213 R¹⁷ R² G¹³ 1214 R¹⁸ R² G¹³ 1215 R¹⁹ R² G¹³ 1216 R²⁰ R² G¹³ 1217 R²¹ R² G¹³ 1218 R²² R² G¹³ 1219 R²³ R² G¹³ 1220 R²⁴ R² G¹³ 1221 R²⁵ R² G¹³ 1222 R²⁶ R² G¹³ 1223 R²⁷ R² G¹³ 1224 R²⁸ R² G¹³ 1225 R²⁹ R² G¹³ 1226 R³⁰ R² G¹³ 1227 R³¹ R² G¹³ 1228 R³² R² G¹³ 1229 R² R³ G¹³ 1230 R² R⁴ G¹³ 1231 R² R⁵ G¹³ 1232 R² R⁶ G¹³ 1233 R² R⁷ G¹³ 1234 R² R⁸ G¹³ 1235 R² R⁹ G¹³ 1236 R² R¹⁰ G¹³ 1237 R² R¹¹ G¹³ 1238 R² R¹² G¹³ 1239 R² R¹³ G¹³ 1240 R² R¹⁴ G¹³ 1241 R² R¹⁵ G¹³ 1242 R² R¹⁶ G¹³ 1243 R² R¹⁷ G¹³ 1244 R² R¹⁸ G¹³ 1245 R² R¹⁹ G¹³ 1246 R² R²⁰ G¹³ 1247 R² R²¹ G¹³ 1248 R² R²² G¹³ 1249 R² R²³ G¹³ 1250 R² R²⁴ G¹³ 1251 R² R²⁵ G¹³ 1252 R² R²⁶ G¹³ 1253 R² R²⁷ G¹³ 1254 R² R²⁸ G¹³ 1255 R² R²⁹ G¹³ 1256 R² R³⁰ G¹³ 1257 R² R³¹ G¹³ 1258 R² R³² G¹³ 1259 R² R³² G¹³ 1260 R³ R³² G¹³ 1261 R⁴ R³² G¹³ 1262 R⁵ R³² G¹³ 1263 R⁶ R³² G¹³ 1264 R⁷ R³² G¹³ 1265 R⁸ R³² G¹³ 1266 R⁹ R³² G¹³ 1267 R¹⁰ R³² G¹³ 1268 R¹¹ R³² G¹³ 1269 R¹² R³² G¹³ 1270 R¹³ R³² G¹³ 1271 R¹⁴ R³² G¹³ 1272 R¹⁵ R³² G¹³ 1273 R¹⁶ R³² G¹³ 1274 R¹⁷ R³² G¹³ 1275 R¹⁸ R³² G¹³ 1276 R¹⁹ R³² G¹³ 1277 R²⁰ R³² G¹³ 1278 R²¹ R³² G¹³ 1279 R²² R³² G¹³ 1280 R²³ R³² G¹³ 1281 R²⁴ R³² G¹³ 1282 R²⁵ R³² G¹³ 1283 R²⁶ R³² G¹³ 1284 R²⁷ R³² G¹³ 1285 R²⁸ R³² G¹³ 1286 R²⁹ R³² G¹³ 1287 R³⁰ R³² G¹³ 1288 R³¹ R³² G¹³ 1289 R³² R² G¹³ 1290 R³² R³ G¹³ 1291 R³² R⁴ G¹³ 1292 R³² R⁵ G¹³ 1293 R³² R⁶ G¹³ 1294 R³² R⁷ G¹³ 1295 R³² R⁸ G¹³ 1296 R³² R⁹ G¹³ 1297 R³² R¹⁰ G¹³ 1298 R³² R¹¹ G¹³ 1299 R³² R¹² G¹³ 1300 R³² R¹³ G¹³ 1301 R³² R¹⁴ G¹³ 1302 R³² R¹⁵ G¹³ 1303 R³² R¹⁶ G¹³ 1304 R³² R¹⁷ G¹³ 1305 R³² R¹⁸ G¹³ 1306 R³² R¹⁹ G¹³ 1307 R³² R²⁰ G¹³ 1308 R³² R²¹ G¹³ 1309 R³² R²² G¹³ 1310 R³² R²³ G¹³ 1311 R³² R²⁴ G¹³ 1312 R³² R²⁵ G¹³ 1313 R³² R²⁶ G¹³ 1314 R³² R²⁷ G¹³ 1315 R³² R²⁸ G¹³ 1316 R³² R²⁹ G¹³ 1317 R³² R³⁰ G¹³ 1318 R³² R³¹ G¹³ 1319 R¹ R³³ G¹¹ 1320 R¹ R³⁴ G¹¹ 1321 R¹ R³⁵ G¹¹ 1322 R¹ R³⁶ G¹¹ 1323 R¹ R³⁷ G¹¹ 1324 R¹ R³⁸ G¹¹ 1325 R¹ R³⁹ G¹¹ 1326 R¹ R⁴⁰ G¹¹ 1327 R¹ R⁴¹ G¹¹ 1328 R³³ R¹ G¹¹ 1329 R³⁴ R¹ G¹¹ 1330 R³⁵ R¹ G¹¹ 1331 R³⁶ R¹ G¹¹ 1332 R³⁷ R¹ G¹¹ 1333 R³⁸ R¹ G¹¹ 1334 R³⁹ R¹ G¹¹ 1335 R⁴⁰ R¹ G¹¹ 1336 R⁴¹ R¹ G¹¹ where R_(E) and R_(F) have the following structures:

wherein G¹ to G¹⁴ have the following structures:

In some embodiments of the compound where the compound has a formula of M(L_(A))_(q)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M, L_(B) and L_(C) can each be independently selected from the group consisting of the Ligand Group C:

where: each Y¹ to Y¹³ are independently selected from the group consisting of carbon and nitrogen; Y′ is selected from the group consisting of BR_(e), NR_(e), PR_(e), O, S, Se, C═O, S═O, SO₂, CR_(e)R_(f), SiR_(e)R_(f), and GeR_(e)R_(f); R_(e) and R_(f) can be fused or joined to form a ring; each R_(a), R_(b), R_(c), and R_(c)i independently represent zero, mono, or up to a maximum allowed substitution to its associated ring; each of R_(a), R_(b), R_(c), R_(d), R_(e) and R_(f) is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) can be fused or joined to form a ring or form a multidentate ligand.

In some embodiments of the compound where the compound has a formula of M(L_(A))_(q)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M, L_(B) and L_(C) can each be independently selected from the group consisting of the Ligand Group D:

In some embodiments of the compound, the compound has a formula of M(L_(A))_(q)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M. In some embodiments, L_(B) is selected from the group consisting of L_(B1) to L_(B263) shown below with general formula of L_(Bk), wherein k is an integer from 1 to 263:

In some embodiments, L_(B) is selected from the group consisting of: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128), L_(B130), L_(B32), L_(B134), L_(B136), L_(B138), L_(B140), L_(B142), L_(B144), L_(B156), L_(B58), L_(B160), L_(B162), L_(B164), L_(B168), L_(B172), L_(B175), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B222), L_(B231), L_(B233), L_(B235), L_(B237), L_(B240), L_(B242), L_(B244), L_(B246), L_(B248), L_(B250), L_(B252), L_(B254), L_(B256), L_(B258), L_(B260), L_(B262), and L_(B263).

In some embodiments, L_(B) is selected from the group consisting of: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128), L_(B132), L_(B136), L_(B138), L_(B142), L_(B156), L_(B162), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B231), L_(B233), and L_(B237).

In some embodiments of the compound having the formula of M(L_(A))_(p)(L_(B))_(q)(L_(C))_(r) where L_(B) and L_(C) are each a bidentate ligand; and where p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M, L_(C) can be selected from the group consisting of L_(Cj-I) and L_(Cj-II), where j is an integer from 1 to 768, wherein L_(Cj-I) consists of the compounds of L_(C1-I) through L_(C768-I) with general numbering formula L_(Cj-I) based on a structure of

and L_(Cj-II) consists of the compounds of L_(C1-II) through LC_(768-II) with general numbering formula L_(Cj-II) based on a structure of

wherein R^(1′) and R^(2′) for L_(Cj-I) and L_(Cj-II) are each independently defined as follows:

Ligand R^(1′) R^(2′) L_(C1) R^(D1) R^(D1) L_(C2) R^(D2) R^(D2) L_(C3) R^(D3) R^(D3) L_(C4) R^(D4) R^(D4) L_(C5) R^(D5) R^(D5) L_(C6) R^(D6) R^(D6) L_(C7) R^(D7) R^(D7) L_(C8) R^(D8) R^(D8) L_(C9) R^(D9) R^(D9) L_(C10) R^(D10) R^(D10) L_(C11) R^(D11) R^(D11) L_(C12) R^(D12) R^(D12) L_(C13) R^(D13) R^(D13) L_(C14) R^(D14) R^(D14) L_(C15) R^(D15) R^(D15) L_(C16) R^(D16) R^(D16) L_(C17) R^(D17) R^(D17) L_(C18) R^(D18) R^(D18) L_(C19) R^(D19) R^(D19) L_(C20) R^(D20) R^(D20) L_(C21) R^(D21) R^(D21) L_(C22) R^(D22) R^(D22) L_(C23) R^(D23) R^(D23) L_(C24) R^(D24) R^(D24) L_(C25) R^(D25) R^(D25) L_(C26) R^(D26) R^(D26) L_(C27) R^(D27) R^(D27) L_(C28) R^(D28) R^(D28) L_(C29) R^(D29) R^(D29) L_(C30) R^(D30) R^(D30) L_(C31) R^(D31) R^(D31) L_(C32) R^(D32) R^(D32) L_(C33) R^(D33) R^(D33) L_(C34) R^(D34) R^(D34) L_(C35) R^(D35) R^(D35) L_(C36) R^(D36) R^(D36) L_(C37) R^(D37) R^(D37) L_(C38) R^(D38) R^(D38) L_(C39) R^(D39) R^(D39) L_(C40) R^(D40) R^(D40) L_(C41) R^(D41) R^(D41) L_(C42) R^(D42) R^(D42) L_(C43) R^(D43) R^(D43) L_(C44) R^(D44) R^(D44) L_(C45) R^(D45) R^(D45) L_(C46) R^(D46) R^(D46) L_(C47) R^(D47) R^(D47) L_(C48) R^(D48) R^(D48) L_(C49) R^(D49) R^(D49) L_(C50) R^(D50) R^(D50) L_(C51) R^(D51) R^(D51) L_(C52) R^(D52) R^(D52) L_(C53) R^(D53) R^(D53) L_(C54) R^(D54) R^(D54) L_(C55) R^(D55) R^(D55) L_(C56) R^(D56) R^(D56) L_(C57) R^(D57) R^(D57) L_(C58) R^(D58) R^(D58) L_(C59) R^(D59) R^(D59) L_(C60) R^(D60) R^(D60) L_(C61) R^(D61) R^(D61) L_(C62) R^(D62) R^(D62) L_(C63) R^(D63) R^(D63) L_(C64) R^(D64) R^(D64) L_(C65) R^(D65) R^(D65) L_(C66) R^(D66) R^(D66) L_(C67) R^(D67) R^(D67) L_(C68) R^(D68) R^(D68) L_(C69) R^(D69) R^(D69) L_(C70) R^(D70) R^(D70) L_(C71) R^(D71) R^(D71) L_(C72) R^(D72) R^(D72) L_(C73) R^(D73) R^(D73) L_(C74) R^(D74) R^(D74) L_(C75) R^(D75) R^(D75) L_(C76) R^(D76) R^(D76) L_(C77) R^(D77) R^(D77) L_(C78) R^(D78) R^(D78) L_(C79) R^(D79) R^(D79) L_(C80) R^(D80) R^(D80) L_(C81) R^(D81) R^(D81) L_(C82) R^(D82) R^(D82) L_(C83) R^(D83) R^(D83) L_(C84) R^(D84) R^(D84) L_(C85) R^(D85) R^(D85) L_(C86) R^(D86) R^(D86) L_(C87) R^(D87) R^(D87) L_(C88) R^(D88) R^(D88) L_(C89) R^(D89) R^(D89) L_(C90) R^(D90) R^(D90) L_(C91) R^(D91) R^(D91) L_(C92) R^(D92) R^(D92) L_(C93) R^(D93) R^(D93) L_(C94) R^(D94) R^(D94) L_(C95) R^(D95) R^(D95) L_(C96) R^(D96) R^(D96) L_(C97) R^(D97) R^(D97) L_(C98) R^(D98) R^(D98) L_(C99) R^(D99) R^(D99) L_(C100) R^(D100) R^(D100) L_(C101) R^(D101) R^(D101) L_(C102) R^(D102) R^(D102) L_(C103) R^(D103) R^(D103) L_(C104) R^(D104) R^(D104) L_(C105) R^(D105) R^(D105) L_(C106) R^(D106) R^(D106) L_(C107) R^(D107) R^(D107) L_(C108) R^(D108) R^(D108) L_(C109) R^(D109) R^(D109) L_(C110) R^(D110) R^(D110) L_(C111) R^(D111) R^(D111) L_(C112) R^(D112) R^(D112) L_(C113) R^(D113) R^(D113) L_(C114) R^(D114) R^(D114) L_(C115) R^(D115) R^(D115) L_(C116) R^(D116) R^(D116) L_(C117) R^(D117) R^(D117) L_(C118) R^(D118) R^(D118) L_(C119) R^(D119) R^(D119) L_(C120) R^(D120) R^(D120) L_(C121) R^(D121) R^(D121) L_(C122) R^(D122) R^(D122) L_(C123) R^(D123) R^(D123) L_(C124) R^(D124) R^(D124) L_(C125) R^(D125) R^(D125) L_(C126) R^(D126) R^(D126) L_(C127) R^(D127) R^(D127) L_(C128) R^(D128) R^(D128) L_(C129) R^(D129) R^(D129) L_(C130) R^(D130) R^(D130) L_(C131) R^(D131) R^(D131) L_(C132) R^(D132) R^(D132) L_(C133) R^(D133) R^(D133) L_(C134) R^(D134) R^(D134) L_(C135) R^(D135) R^(D135) L_(C136) R^(D136) R^(D136) L_(C137) R^(D137) R^(D137) L_(C138) R^(D138) R^(D138) L_(C139) R^(D139) R^(D139) L_(C140) R^(D140) R^(D140) L_(C141) R^(D141) R^(D141) L_(C142) R^(D142) R^(D142) L_(C143) R^(D143) R^(D143) L_(C144) R^(D144) R^(D144) L_(C145) R^(D145) R^(D145) L_(C146) R^(D146) R^(D146) L_(C147) R^(D147) R^(D147) L_(C148) R^(D148) R^(D148) L_(C149) R^(D149) R^(D149) L_(C150) R^(D150) R^(D150) L_(C151) R^(D151) R^(D151) L_(C152) R^(D152) R^(D152) L_(C153) R^(D153) R^(D153) L_(C154) R^(D154) R^(D154) L_(C155) R^(D155) R^(D155) L_(C156) R^(D156) R^(D156) L_(C157) R^(D157) R^(D157) L_(C158) R^(D158) R^(D158) L_(C159) R^(D159) R^(D159) L_(C160) R^(D160) R^(D160) L_(C161) R^(D161) R^(D161) L_(C162) R^(D162) R^(D162) L_(C163) R^(D163) R^(D163) L_(C164) R^(D164) R^(D164) L_(C165) R^(D165) R^(D165) L_(C166) R^(D166) R^(D166) L_(C167) R^(D167) R^(D167) L_(C168) R^(D168) R^(D168) L_(C169) R^(D169) R^(D169) L_(C170) R^(D170) R^(D170) L_(C171) R^(D171) R^(D171) L_(C172) R^(D172) R^(D172) L_(C173) R^(D173) R^(D173) L_(C174) R^(D174) R^(D174) L_(C175) R^(D175) R^(D175) L_(C176) R^(D176) R^(D176) L_(C177) R^(D177) R^(D177) L_(C178) R^(D178) R^(D178) L_(C179) R^(D179) R^(D179) L_(C180) R^(D180) R^(D180) L_(C181) R^(D181) R^(D181) L_(C182) R^(D182) R^(D182) L_(C183) R^(D183) R^(D183) L_(C184) R^(D184) R^(D184) L_(C185) R^(D185) R^(D185) L_(C186) R^(D186) R^(D186) L_(C187) R^(D187) R^(D187) L_(C188) R^(D188) R^(D188) L_(C189) R^(D189) R^(D189) L_(C190) R^(D190) R^(D190) L_(C191) R^(D191) R^(D191) L_(C192) R^(D192) R^(D192) L_(C193) R^(D1) R^(D3) L_(C194) R^(D1) R^(D4) L_(C195) R^(D1) R^(D5) L_(C196) R^(D1) R^(D9) L_(C197) R^(D1) R^(D10) L_(C198) R^(D1) R^(D17) L_(C199) R^(D1) R^(D18) L_(C200) R^(D1) R^(D20) L_(C201) R^(D1) R^(D22) L_(C202) R^(D1) R^(D37) L_(C203) R^(D1) R^(D40) L_(C204) R^(D1) R^(D41) L_(C205) R^(D1) R^(D42) L_(C206) R^(D1) R^(D43) L_(C207) R^(D1) R^(D48) L_(C208) R^(D1) R^(D49) L_(C209) R^(D1) R^(D50) L_(C210) R^(D1) R^(D54) L_(C211) R^(D1) R^(D55) L_(C212) R^(D1) R^(D58) L_(C213) R^(D1) R^(D59) L_(C214) R^(D1) R^(D78) L_(C215) R^(D1) R^(D79) L_(C216) R^(D1) R^(D81) L_(C217) R^(D1) R^(D87) L_(C218) R^(D1) R^(D88) L_(C219) R^(D1) R^(D89) L_(C220) R^(D1) R^(D93) L_(C221) R^(D1) R^(D116) L_(C222) R^(D1) R^(D117) L_(C223) R^(D1) R^(D118) L_(C224) R^(D1) R^(D119) L_(C225) R^(D1) R^(D120) L_(C226) R^(D1) R^(D133) L_(C227) R^(D1) R^(D134) L_(C228) R^(D1) R^(D135) L_(C229) R^(D1) R^(D136) L_(C230) R^(D1) R^(D143) L_(C231) R^(D1) R^(D144) L_(C232) R^(D1) R^(D145) L_(C233) R^(D1) R^(D146) L_(C234) R^(D1) R^(D147) L_(C235) R^(D1) R^(D149) L_(C236) R^(D1) R^(D151) L_(C237) R^(D1) R^(D154) L_(C238) R^(D1) R^(D155) L_(C239) R^(D1) R^(D161) L_(C240) R^(D1) R^(D175) L_(C241) R^(D4) R^(D3) L_(C242) R^(D4) R^(D5) L_(C243) R^(D4) R^(D9) L_(C244) R^(D4) R^(D10) L_(C245) R^(D4) R^(D17) L_(C246) R^(D4) R^(D18) L_(C247) R^(D4) R^(D20) L_(C248) R^(D4) R^(D22) L_(C249) R^(D4) R^(D37) L_(C250) R^(D4) R^(D40) L_(C251) R^(D4) R^(D41) L_(C252) R^(D4) R^(D42) L_(C253) R^(D4) R^(D43) L_(C254) R^(D4) R^(D48) L_(C255) R^(D4) R^(D49) L_(C256) R^(D4) R^(D50) L_(C257) R^(D4) R^(D54) L_(C258) R^(D4) R^(D55) L_(C259) R^(D4) R^(D58) L_(C260) R^(D4) R^(D59) L_(C261) R^(D4) R^(D78) L_(C262) R^(D4) R^(D79) L_(C263) R^(D4) R^(D51) L_(C264) R^(D4) R^(D87) L_(C265) R^(D4) R^(D88) L_(C266) R^(D4) R^(D89) L_(C267) R^(D4) R^(D93) L_(C268) R^(D4) R^(D116) L_(C269) R^(D4) R^(D117) L_(C270) R^(D4) R^(D118) L_(C271) R^(D4) R^(D119) L_(C272) R^(D4) R^(D120) L_(C273) R^(D4) R^(D133) L_(C274) R^(D4) R^(D134) L_(C275) R^(D4) R^(D135) L_(C276) R^(D4) R^(D136) L_(C277) R^(D4) R^(D143) L_(C278) R^(D4) R^(D144) L_(C279) R^(D4) R^(D145) L_(C280) R^(D4) R^(D146) L_(C281) R^(D4) R^(D147) L_(C282) R^(D4) R^(D149) L_(C283) R^(D4) R^(D151) L_(C284) R^(D4) R^(D154) L_(C285) R^(D4) R^(D155) L_(C286) R^(D4) R^(D161) L_(C287) R^(D4) R^(D175) L_(C288) R^(D9) R^(D3) L_(C289) R^(D9) R^(D5) L_(C290) R^(D9) R^(D10) L_(C291) R^(D9) R^(D17) L_(C292) R^(D9) R^(D38) L_(C293) R^(D9) R^(D20) L_(C294) R^(D9) R^(D22) L_(C295) R^(D9) R^(D37) L_(C296) R^(D9) R^(D40) L_(C297) R^(D9) R^(D41) L_(C298) R^(D9) R^(D42) L_(C299) R^(D9) R^(D43) L_(C300) R^(D9) R^(D48) L_(C301) R^(D9) R^(D49) L_(C302) R^(D9) R^(D50) L_(C303) R^(D9) R^(D54) L_(C304) R^(D9) R^(D55) L_(C305) R^(D9) R^(D58) L_(C306) R^(D9) R^(D59) L_(C307) R^(D9) R^(D78) L_(C308) R^(D9) R^(D79) L_(C309) R^(D9) R^(D81) L_(C310) R^(D9) R^(D87) L_(C311) R^(D9) R^(D88) L_(C312) R^(D9) R^(D89) L_(C313) R^(D9) R^(D93) L_(C314) R^(D9) R^(D116) L_(C315) R^(D9) R^(D117) L_(C316) R^(D9) R^(D118) L_(C317) R^(D9) R^(D119) L_(C318) R^(D9) R^(D120) L_(C319) R^(D9) R^(D133) L_(C320) R^(D9) R^(D134) L_(C321) R^(D9) R^(D135) L_(C322) R^(D9) R^(D136) L_(C323) R^(D9) R^(D143) L_(C324) R^(D9) R^(D144) L_(C325) R^(D9) R^(D145) L_(C326) R^(D9) R^(D146) L_(C327) R^(D9) R^(D147) L_(C328) R^(D9) R^(D149) L_(C329) R^(D9) R^(D151) L_(C330) R^(D9) R^(D154) L_(C331) R^(D9) R^(D155) L_(C332) R^(D9) R^(D161) L_(C333) R^(D9) R^(D175) L_(C334) R^(D10) R^(D3) L_(C335) R^(D10) R^(D5) L_(C336) R^(D10) R^(D17) L_(C337) R^(D10) R^(D18) L_(C338) R^(D10) R^(D20) L_(C339) R^(D10) R^(D22) L_(C340) R^(D10) R^(D37) L_(C341) R^(D10) R^(D40) L_(C342) R^(D10) R^(D41) L_(C343) R^(D10) R^(D42) L_(C344) R^(D10) R^(D43) L_(C345) R^(D10) R^(D48) L_(C346) R^(D10) R^(D49) L_(C347) R^(D10) R^(D50) L_(C348) R^(D10) R^(D54) L_(C349) R^(D10) R^(D55) L_(C350) R^(D10) R^(D58) L_(C351) R^(D10) R^(D59) L_(C352) R^(D10) R^(D78) L_(C353) R^(D10) R^(D79) L_(C354) R^(D10) R^(D81) L_(C355) R^(D10) R^(D87) L_(C356) R^(D10) R^(D88) L_(C357) R^(D10) R^(D89) L_(C358) R^(D10) R^(D93) L_(C359) R^(D10) R^(D116) L_(C360) R^(D10) R^(D117) L_(C361) R^(D10) R^(D118) L_(C362) R^(D10) R^(D119) L_(C363) R^(D10) R^(D120) L_(C364) R^(D10) R^(D133) L_(C365) R^(D10) R^(D134) L_(C366) R^(D10) R^(D135) L_(C367) R^(D10) R^(D136) L_(C368) R^(D10) R^(D143) L_(C369) R^(D10) R^(D144) L_(C370) R^(D10) R^(D145) L_(C371) R^(D10) R^(D146) L_(C372) R^(D10) R^(D147) L_(C373) R^(D10) R^(D149) L_(C374) R^(D10) R^(D151) L_(C375) R^(D10) R^(D154) L_(C376) R^(D10) R^(D155) L_(C377) R^(D10) R^(D161) L_(C378) R^(D10) R^(D175) L_(C379) R^(D17) R^(D3) L_(C380) R^(D17) R^(D5) L_(C381) R^(D17) R^(D38) L_(C382) R^(D17) R^(D20) L_(C383) R^(D17) R^(D22) L_(C384) R^(D17) R^(D37) L_(C385) R^(D17) R^(D40) L_(C386) R^(D17) R^(D41) L_(C387) R^(D17) R^(D42) L_(C388) R^(D17) R^(D43) L_(C389) R^(D17) R^(D48) L_(C390) R^(D17) R^(D49) L_(C391) R^(D17) R^(D50) L_(C392) R^(D17) R^(D54) L_(C393) R^(D17) R^(D55) L_(C394) R^(D17) R^(D58) L_(C395) R^(D17) R^(D59) L_(C396) R^(D17) R^(D78) L_(C397) R^(D17) R^(D79) L_(C398) R^(D17) R^(D81) L_(C399) R^(D17) R^(D87) L_(C400) R^(D17) R^(D88) L_(C401) R^(D17) R^(D89) L_(C402) R^(D17) R^(D93) L_(C403) R^(D17) R^(D116) L_(C404) R^(D17) R^(D117) L_(C405) R^(D17) R^(D118) L_(C406) R^(D17) R^(D119) L_(C407) R^(D17) R^(D120) L_(C408) R^(D17) R^(D133) L_(C409) R^(D17) R^(D134) L_(C410) R^(D17) R^(D135) L_(C411) R^(D17) R^(D136) L_(C412) R^(D17) R^(D143) L_(C413) R^(D17) R^(D144) L_(C414) R^(D17) R^(D145) L_(C415) R^(D17) R^(D146) L_(C416) R^(D17) R^(D147) L_(C417) R^(D17) R^(D149) L_(C418) R^(D17) R^(D151) L_(C419) R^(D17) R^(D154) L_(C420) R^(D17) R^(D155) L_(C421) R^(D17) R^(D161) L_(C422) R^(D17) R^(D175) L_(C423) R^(D50) R^(D3) L_(C424) R^(D50) R^(D5) L_(C425) R^(D50) R^(D18) L_(C426) R^(D50) R^(D20) L_(C427) R^(D50) R^(D22) L_(C428) R^(D50) R^(D37) L_(C429) R^(D50) R^(D40) L_(C430) R^(D50) R^(D41) L_(C431) R^(D50) R^(D42) L_(C432) R^(D50) R^(D43) L_(C433) R^(D50) R^(D48) L_(C434) R^(D50) R^(D49) L_(C435) R^(D50) R^(D54) L_(C436) R^(D50) R^(D55) L_(C437) R^(D50) R^(D58) L_(C438) R^(D50) R^(D59) L_(C439) R^(D50) R^(D78) L_(C440) R^(D50) R^(D79) L_(C441) R^(D50) R^(D81) L_(C442) R^(D50) R^(D87) L_(C443) R^(D50) R^(D88) L_(C444) R^(D50) R^(D89) L_(C445) R^(D50) R^(D93) L_(C446) R^(D50) R^(D116) L_(C447) R^(D50) R^(D117) L_(C448) R^(D50) R^(D118) L_(C449) R^(D50) R^(D119) L_(C450) R^(D50) R^(D120) L_(C451) R^(D50) R^(D133) L_(C452) R^(D50) R^(D134) L_(C453) R^(D50) R^(D135) L_(C454) R^(D50) R^(D136) L_(C455) R^(D50) R^(D143) L_(C456) R^(D50) R^(D144) L_(C457) R^(D50) R^(D145) L_(C458) R^(D50) R^(D146) L_(C459) R^(D50) R^(D147) L_(C460) R^(D50) R^(D149) L_(C461) R^(D50) R^(D151) L_(C462) R^(D50) R^(D154) L_(C463) R^(D50) R^(D155) L_(C464) R^(D50) R^(D161) L_(C465) R^(D50) R^(D175) L_(C466) R^(D55) R^(D3) L_(C467) R^(D55) R^(D5) L_(C468) R^(D55) R^(D18) L_(C469) R^(D55) R^(D20) L_(C470) R^(D55) R^(D22) L_(C471) R^(D55) R^(D37) L_(C472) R^(D55) R^(D40) L_(C473) R^(D55) R^(D41) L_(C474) R^(D55) R^(D42) L_(C475) R^(D55) R^(D43) L_(C476) R^(D55) R^(D48) L_(C477) R^(D55) R^(D49) L_(C478) R^(D55) R^(D54) L_(C479) R^(D55) R^(D58) L_(C480) R^(D55) R^(D59) L_(C481) R^(D55) R^(D78) L_(C482) R^(D55) R^(D79) L_(C483) R^(D55) R^(D81) L_(C484) R^(D55) R^(D87) L_(C485) R^(D55) R^(D88) L_(C486) R^(D55) R^(D89) L_(C487) R^(D55) R^(D93) L_(C488) R^(D55) R^(D116) L_(C489) R^(D55) R^(D117) L_(C490) R^(D55) R^(D118) L_(C491) R^(D55) R^(D119) L_(C492) R^(D55) R^(D120) L_(C493) R^(D55) R^(D133) L_(C494) R^(D55) R^(D134) L_(C495) R^(D55) R^(D135) L_(C496) R^(D55) R^(D136) L_(C497) R^(D55) R^(D143) L_(C498) R^(D55) R^(D144) L_(C499) R^(D55) R^(D145) L_(C500) R^(D55) R^(D146) L_(C501) R^(D55) R^(D147) L_(C502) R^(D55) R^(D149) L_(C503) R^(D55) R^(D151) L_(C504) R^(D55) R^(D154) L_(C505) R^(D55) R^(D155) L_(C506) R^(D55) R^(D161) L_(C507) R^(D55) R^(D175) L_(C508) R^(D116) R^(D3) L_(C509) R^(D116) R^(D5) L_(C510) R^(D116) R^(D17) L_(C511) R^(D116) R^(D18) L_(C512) R^(D116) R^(D20) L_(C513) R^(D116) R^(D22) L_(C514) R^(D116) R^(D37) L_(C515) R^(D116) R^(D40) L_(C516) R^(D116) R^(D41) L_(C517) R^(D116) R^(D42) L_(C518) R^(D116) R^(D43) L_(C519) R^(D116) R^(D48) L_(C520) R^(D116) R^(D49) L_(C521) R^(D116) R^(D54) L_(C522) R^(D116) R^(D58) L_(C523) R^(D116) R^(D59) L_(C524) R^(D116) R^(D78) L_(C525) R^(D116) R^(D79) L_(C526) R^(D116) R^(D81) L_(C527) R^(D116) R^(D87) L_(C528) R^(D116) R^(D88) L_(C529) R^(D116) R^(D89) L_(C530) R^(D116) R^(D93) L_(C531) R^(D116) R^(D117) L_(C532) R^(D116) R^(D118) L_(C533) R^(D116) R^(D119) L_(C534) R^(D116) R^(D120) L_(C535) R^(D116) R^(D133) L_(C536) R^(D116) R^(D134) L_(C537) R^(D116) R^(D135) L_(C538) R^(D116) R^(D136) L_(C539) R^(D116) R^(D143) L_(C540) R^(D116) R^(D144) L_(C541) R^(D116) R^(D145) L_(C542) R^(D116) R^(D146) L_(C543) R^(D116) R^(D147) L_(C544) R^(D116) R^(D149) L_(C545) R^(D116) R^(D151) L_(C546) R^(D116) R^(D154) L_(C547) R^(D116) R^(D155) L_(C548) R^(D116) R^(D161) L_(C549) R^(D116) R^(D175) L_(C550) R^(D143) R^(D3) L_(C551) R^(D143) R^(D5) L_(C552) R^(D143) R^(D17) L_(C553) R^(D143) R^(D18) L_(C554) R^(D143) R^(D20) L_(C555) R^(D143) R^(D22) L_(C556) R^(D143) R^(D37) L_(C557) R^(D143) R^(D40) L_(C558) R^(D143) R^(D41) L_(C559) R^(D143) R^(D42) L_(C560) R^(D143) R^(D43) L_(C561) R^(D143) R^(D48) L_(C562) R^(D143) R^(D49) L_(C563) R^(D143) R^(D54) L_(C564) R^(D143) R^(D58) L_(C565) R^(D143) R^(D59) L_(C566) R^(D143) R^(D78) L_(C567) R^(D143) R^(D79) L_(C568) R^(D143) R^(D81) L_(C569) R^(D143) R^(D87) L_(C570) R^(D143) R^(D88) L_(C571) R^(D143) R^(D89) L_(C572) R^(D143) R^(D93) L_(C573) R^(D143) R^(D116) L_(C574) R^(D143) R^(D117) L_(C575) R^(D143) R^(D118) L_(C576) R^(D143) R^(D119) L_(C577) R^(D143) R^(D120) L_(C578) R^(D143) R^(D133) L_(C579) R^(D143) R^(D134) L_(C580) R^(D143) R^(D135) L_(C581) R^(D143) R^(D136) L_(C582) R^(D143) R^(D144) L_(C583) R^(D143) R^(D145) L_(C584) R^(D143) R^(D146) L_(C585) R^(D143) R^(D147) L_(C586) R^(D143) R^(D149) L_(C587) R^(D143) R^(D151) L_(C588) R^(D143) R^(D154) L_(C589) R^(D143) R^(D155) L_(C590) R^(D143) R^(D161) L_(C591) R^(D143) R^(D175) L_(C592) R^(D144) R^(D3) L_(C593) R^(D144) R^(D5) L_(C594) R^(D144) R^(D17) L_(C595) R^(D144) R^(D18) L_(C596) R^(D144) R^(D20) L_(C597) R^(D144) R^(D22) L_(C598) R^(D144) R^(D37) L_(C599) R^(D144) R^(D40) L_(C600) R^(D144) R^(D41) L_(C601) R^(D144) R^(D42) L_(C602) R^(D144) R^(D43) L_(C603) R^(D144) R^(D48) L_(C604) R^(D144) R^(D49) L_(C605) R^(D144) R^(D54) L_(C606) R^(D144) R^(D58) L_(C607) R^(D144) R^(D59) L_(C608) R^(D144) R^(D78) L_(C609) R^(D144) R^(D79) L_(C610) R^(D144) R^(D81) L_(C611) R^(D144) R^(D87) L_(C612) R^(D144) R^(D88) L_(C613) R^(D144) R^(D89) L_(C614) R^(D144) R^(D93) L_(C615) R^(D144) R^(D116) L_(C616) R^(D144) R^(D117) L_(C617) R^(D144) R^(D118) L_(C618) R^(D144) R^(D119) L_(C619) R^(D144) R^(D120) L_(C620) R^(D144) R^(D133) L_(C621) R^(D144) R^(D134) L_(C622) R^(D144) R^(D135) L_(C623) R^(D144) R^(D136) L_(C624) R^(D144) R^(D145) L_(C625) R^(D144) R^(D146) L_(C626) R^(D144) R^(D147) L_(C627) R^(D144) R^(D149) L_(C628) R^(D144) R^(D151) L_(C629) R^(D144) R^(D154) L_(C630) R^(D144) R^(D155) L_(C631) R^(D144) R^(D161) L_(C632) R^(D144) R^(D175) L_(C633) R^(D145) R^(D3) L_(C634) R^(D145) R^(D5) L_(C635) R^(D145) R^(D17) L_(C636) R^(D145) R^(D18) L_(C637) R^(D145) R^(D20) L_(C638) R^(D145) R^(D22) L_(C639) R^(D145) R^(D37) L_(C640) R^(D145) R^(D40) L_(C641) R^(D145) R^(D41) L_(C642) R^(D145) R^(D42) L_(C643) R^(D145) R^(D43) L_(C644) R^(D145) R^(D48) L_(C645) R^(D145) R^(D49) L_(C646) R^(D145) R^(D54) L_(C647) R^(D145) R^(D58) L_(C648) R^(D145) R^(D59) L_(C649) R^(D145) R^(D78) L_(C650) R^(D145) R^(D79) L_(C651) R^(D145) R^(D81) L_(C652) R^(D145) R^(D87) L_(C653) R^(D145) R^(D88) L_(C654) R^(D145) R^(D89) L_(C655) R^(D145) R^(D93) L_(C656) R^(D145) R^(D116) L_(C657) R^(D145) R^(D117) L_(C658) R^(D145) R^(D118) L_(C659) R^(D145) R^(D119) L_(C660) R^(D145) R^(D120) L_(C661) R^(D145) R^(D133) L_(C662) R^(D145) R^(D134) L_(C663) R^(D145) R^(D135) L_(C664) R^(D145) R^(D136) L_(C665) R^(D145) R^(D146) L_(C666) R^(D145) R^(D147) L_(C667) R^(D145) R^(D149) L_(C668) R^(D145) R^(D151) L_(C669) R^(D145) R^(D154) L_(C670) R^(D145) R^(D155) L_(C671) R^(D145) R^(D161) L_(C672) R^(D145) R^(D175) L_(C673) R^(D146) R^(D3) L_(C674) R^(D146) R^(D5) L_(C675) R^(D146) R^(D17) L_(C676) R^(D146) R^(D38) L_(C677) R^(D146) R^(D20) L_(C678) R^(D146) R^(D22) L_(C679) R^(D146) R^(D37) L_(C680) R^(D146) R^(D40) L_(C681) R^(D146) R^(D41) L_(C682) R^(D146) R^(D42) L_(C683) R^(D146) R^(D43) L_(C684) R^(D146) R^(D48) L_(C685) R^(D146) R^(D49) L_(C686) R^(D146) R^(D54) L_(C687) R^(D146) R^(D58) L_(C688) R^(D146) R^(D59) L_(C689) R^(D146) R^(D78) L_(C690) R^(D146) R^(D79) L_(C691) R^(D146) R^(D81) L_(C692) R^(D146) R^(D87) L_(C693) R^(D146) R^(D88) L_(C694) R^(D146) R^(D89) L_(C695) R^(D146) R^(D93) L_(C696) R^(D146) R^(D117) L_(C697) R^(D146) R^(D118) L_(C698) R^(D146) R^(D119) L_(C699) R^(D146) R^(D120) L_(C700) R^(D146) R^(D133) L_(C701) R^(D146) R^(D134) L_(C702) R^(D146) R^(D135) L_(C703) R^(D146) R^(D136) L_(C704) R^(D146) R^(D146) L_(C705) R^(D146) R^(D147) L_(C706) R^(D146) R^(D149) L_(C707) R^(D146) R^(D151) L_(C708) R^(D146) R^(D154) L_(C709) R^(D146) R^(D155) L_(C710) R^(D146) R^(D161) L_(C711) R^(D146) R^(D175) L_(C712) R^(D133) R^(D3) L_(C713) R^(D133) R^(D5) L_(C714) R^(D133) R^(D3) L_(C715) R^(D133) R^(D18) L_(C716) R^(D133) R^(D20) L_(C717) R^(D133) R^(D22) L_(C718) R^(D133) R^(D37) L_(C719) R^(D133) R^(D40) L_(C720) R^(D133) R^(D41) L_(C721) R^(D133) R^(D42) L_(C722) R^(D133) R^(D43) L_(C723) R^(D133) R^(D48) L_(C724) R^(D133) R^(D49) L_(C725) R^(D133) R^(D54) L_(C726) R^(D133) R^(D58) L_(C727) R^(D133) R^(D59) L_(C728) R^(D133) R^(D78) L_(C729) R^(D133) R^(D79) L_(C730) R^(D133) R^(D81) L_(C731) R^(D133) R^(D87) L_(C732) R^(D133) R^(D88) L_(C733) R^(D133) R^(D89) L_(C734) R^(D133) R^(D93) L_(C735) R^(D133) R^(D117) L_(C736) R^(D133) R^(D118) L_(C737) R^(D133) R^(D119) L_(C738) R^(D133) R^(D120) L_(C739) R^(D133) R^(D133) L_(C740) R^(D133) R^(D134) L_(C741) R^(D133) R^(D135) L_(C742) R^(D133) R^(D136) L_(C743) R^(D133) R^(D146) L_(C744) R^(D133) R^(D147) L_(C745) R^(D133) R^(D149) L_(C746) R^(D133) R^(D151) L_(C747) R^(D133) R^(D154) L_(C748) R^(D133) R^(D155) L_(C749) R^(D133) R^(D161) L_(C750) R^(D133) R^(D175) L_(C751) R^(D175) R^(D3) L_(C752) R^(D175) R^(D5) L_(C753) R^(D175) R^(D18) L_(C754) R^(D175) R^(D20) L_(C755) R^(D175) R^(D22) L_(C756) R^(D175) R^(D37) L_(C757) R^(D175) R^(D40) L_(C758) R^(D175) R^(D41) L_(C759) R^(D175) R^(D42) L_(C760) R^(D175) R^(D43) L_(C761) R^(D175) R^(D48) L_(C762) R^(D175) R^(D49) L_(C763) R^(D175) R^(D54) L_(C764) R^(D175) R^(D58) L_(C765) R^(D175) R^(D59) L_(C766) R^(D175) R^(D78) L_(C767) R^(D175) R^(D79) L_(C768) R^(D175) R^(D81)

In some embodiments of the compound, the ligands L_(Cj-I) and L_(Cj-II) consist of only those ligands whose corresponding R¹ and R² are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D10), R^(D17), R^(D18), R^(D20), R^(D22), R^(D37), R^(D40), R^(D41), R^(D42), R^(D43), R^(D48), R^(D49), R^(D50), R^(D54), R^(D55), R^(D58), R^(D59), R^(D78), R^(D79), R^(D81), R^(D87), R^(D88), R^(D89), R^(D93), R^(D116), R^(D117), R^(D118), R^(D119), R^(D120), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D147), R^(D149), R^(D151), R^(D154), R^(D155), R^(D161), R^(D175), and R^(D190).

In some embodiments of the compound, the ligands L_(Cj-I) and L_(Cj-II) consist of only those ligands whose corresponding R^(1′) and R^(2′) are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D17), R^(D22), R^(D43), R^(D50), R^(D78), R^(D116), R^(D118), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D149), R^(D151), R^(D154), R^(D155), R^(D190).

In some embodiments of the compound, the ligand L_(C) is selected from the group consisting of:

In some embodiments of the compound, the compound has a formula selected from the group consisting of Ir(L_(A))₃, Ir(L_(A))(L_(B))₂, Ir(L_(A))₂(L_(B)), Ir(L_(A))₂(L_(C)), and Ir(L_(A))(L_(B))(L_(C)); and where L_(A), L_(b), and L_(C) are different from each other and L_(B) can be selected from the group consisting of L_(B)I to L_(B263) defined herein, and L_(C) can be selected from the group consisting of L_(Cj-I) and L_(Cj-II), where j is an integer from 1 to 768, where L_(Cj-I) consists of the compounds of L_(C1-I) through L_(C768-I) defined herein, and where L_(Cj-II) consists of the compounds of L_(C1-n) through L_(C768-II) defined herein.

In some embodiments of the compound, the compound has a formula of Pt(L_(A))(L_(B)); and where L_(A) and L_(B) can be same or different and L_(B) can be selected from the group consisting of L_(B1) to L_(B263), defined herein. In some embodiments, L_(A) and L_(B) are connected to form a tetradentate ligand.

In some embodiments the compound is selected from the group consisting of Ir(L_(Ai-1))₃ to Ir(L_(A1336-35))₃ based on general formula Ir(L_(Ai-m))₃, Ir(L_(A1-1))(L_(B1))₂ to Ir(L_(A1336-35))(L_(B263))₂ based on general formula of Ir(L_(Ai-m))(L_(Bk))₂, Ir(L_(A1-1))₂(L_(C1-I)) to Ir(L_(A1336-35))₂(L_(C768-I)) based on general formula Ir(L_(Ai-m))₂(L_(Cj-I)), and Ir(L_(A1-1))₂(L_(C1-II)) to Ir(L_(A1136-35))₂(L_(C768-II)) based on general formula Ir(L_(Ai-m))₂(L_(Cj-II)), wherein i is an integer from 1 to 1336, m is an integer from 1 to 35, j is an integer from 1 to 768, k is an integer from 1 to 263, wherein each L_(Ai-m), L_(Bk), L_(Cj-I), and L_(Cj-II) are as defined above.

In some embodiments of the compound, only the following structures among L_(Bk) are included: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128), L_(B130), L_(B32), L_(B134), L_(B136), L_(B138), L_(B140), L_(B142), L_(B144), L_(B155), L_(B58), L_(B160), L_(B162), L_(B164), L_(B168), L_(B172), L_(B175), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B222), L_(B231), L_(B233), L_(B235), L_(B237), L_(B240), L_(B242), L_(B244), L_(B246), L_(B248), L_(B250), L_(B252), L_(B254), L_(B255), L_(B258), L_(B260), and L_(B262).

In some embodiments of the compound, only the following structures among L_(Bk) are included: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B126), L_(B128), L_(B132), L_(B136), L_(B138), L_(B142), L_(B155), L_(B162), L_(B204), L_(B205), L_(B214), L_(B215), L_(B218), L_(B220), L_(B231), L_(B233), and L_(B237).

In some embodiments of the compound, only those L_(Cj-I) and L_(Cj-II) structures in which the corresponding R^(1′) and R^(2′) are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D10), R^(D17), R^(D18), R^(D20), R^(D22), R^(D37), R^(D40), R^(D41), R^(D42), R^(D43), R^(D48), R^(D49), R^(D50), R^(D54), R^(D55), R^(D58), R^(D59), R^(D78), R^(D79), R^(D81), R^(D87), R^(D88), R^(D89), R^(D93), R^(D116), R^(D117), R^(D118), R^(D119), R^(D120), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D147), R^(D149), R^(D151), R^(D154), R^(D155), R^(D161), R^(D175), and R^(D190) that are defined herein, are included.

In some embodiments of the compound, only those L_(Cj-I) and L_(Cj-II) structures in which the corresponding R^(1′) and R^(2′) are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D17), R^(D22), R^(D43), R^(D50), R^(D78), R^(D116), R_(D118), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D149), R^(D151), R^(D154), R^(D155), and R^(D190) that are defined herein, are included.

In some embodiments of the compound that comprises ligand L_(Cj-I), only the following structures among L_(Cj-I) are included: L_(C1-1), L_(C4-1), L_(C9-1), L_(C10-1), L_(C17-1), L_(C50-1), L_(C55-1), L_(C116-1), L_(C143-1), L_(C144-1), L_(C145-1), L_(C190-1), L_(C230-1), L_(C231-1), L_(C232-1), L_(C277-1), L_(C278-1), L_(C279-1), L_(C325-1), L_(C412-1), L_(C413-1) L_(C414-1), and L_(C457-1), defined herein.

In some embodiments, the compound is selected from the group consisting of:

In some embodiments, the compound is selected from the group consisting of:

In another aspect, the compound is selected from the group consisting of:

The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure. In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV:

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C, N, and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V

where indicated by “

”; x⁵ to X¹² are each independently C or N; the maximum number of N within a ring is two; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two substituents can be joined or fused to form a ring; the ligand L_(A) is complexed to a metal M through the two indicated dash lines of each Formula; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being reliable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.

In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, published on Mar. 14, 2019 as U.S. patent application publication No. 2019/0081248, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others).

When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligand(s). In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.

In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter

In some embodiments, the compound of the present disclosure is neutrally charged.

According to another aspect, a formulation comprising the compound described herein is also disclosed.

The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁-Ar₂, and C_(n)H_(2n)—Ar₁, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar₁ and Ar₂ can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound, for example, a Zn containing inorganic material e.g. ZnS.

The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the Host Group consisting of:

and combinations thereof. Additional information on possible hosts is provided below.

In some embodiments, the emissive region may comprise a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV:

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring: X¹ to X⁴ are each independently selected from the group consisting of C, N, and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V

where indicated by “

”; X⁵ to X¹² are each independently C or N; the maximum number of N within a ring is two; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form a ring; the ligand L_(A) is complexed to a metal M through the two indicated dash lines of each Formula; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments of the emissive region, the compound can be an emissive dopant or a non-emissive dopant.

In some embodiments of the emissive region, the emissive region further comprises a host, wherein host contains at least one chemical group selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

In some embodiments, the host may be selected from the group consisting of the HOST Group defined herein.

According to another aspect, a consumer product comprising an OLED is disclosed, wherein the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a ligand L_(A) of Formula I, Formula II, Formula III, or Formula IV:

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C, N, and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V

where indicated by “

”; X⁵ to X¹² are each independently C or N; the maximum number of N within a ring is two; Z and Y are each independently selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form a ring; the ligand L_(A) is complexed to a metal M through the two indicated dash lines of each Formula; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.

The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound is can also be incorporated into the supramolecule complex without covalent bonds.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.

Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH) or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independently selected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is abidentate ligand, Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above, k is an integer from 0 to 20 or 1 to 20. X¹⁰¹ to X¹⁰⁸ are independently selected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² are independently selected from NR¹⁰¹, O, or S.

Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995. U.S. Pat. No. 9,466,803,

Additional Emitters:

One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹ to Ar³ has the similar definition as Ar's mentioned above, k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.

EXPERIMENTALS Synthesis of the Inventive Example Compound 1 with Formula of Ir(L_(A66-1))₂L_(C17)

Solution of 1-(4-(tert-butyl)naphthalen-2-yl)-8-isobutylbenzo[4,5]thieno[2,3-c]pyri-dine (8.43 g, 19.9 mmol, 2.1 equiv) in 2-ethoxyethanol (125 mL) and deionized ultra-filtered (DIUF) water (80 mL) was sparged with nitrogen for 10 minutes. Iridium chloride(III) hydrate (3.019 g, 9.54 mmol, 1.0 equiv) was added and the reaction mixture heated at 95° C. for 18 hours. The solution was cooled to 50° C., the solids were filtered, washed with DIUF water (125 mL) and methanol (125 mL) then air-dried to give solvent wet di-μ-chloro-tetrakis-[(1-(4-(tert-butyl)naphthalen-2-yl)-1-yl)-8-iso-butylbenzo[4,5]thieno[2,3-c]pyridin-6-yl]diiridium(III).

Next, to a solution of di-μ-chloro-tetrakis-[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-isobutyl benzo[4,5]thieno[2,3-c]pyridin-6-yl]iridium(III) (10.23 g, 4.77 mmol, 1.0 equiv) in 2-ethoxyethanol (150 mL) was added, via syringe, 3,7-di-ethylnonane-4,6-dione (5.516 g, 26.0 mmol, 5.45 equiv) and the reaction mixture sparged with nitrogen for 15 minutes. Powdered potassium carbonate (5.317 g, 38.5 mmol, 8.07 equiv) was added and the reaction mixture stirred at room temperature for 72 hours. DIUF water (150 mL) was added and the mixture stirred for 30 minutes. The suspension was filtered, the solid washed with DIUF water (250 mL) and methanol (200 mL) then air-dried. The crude red solid (16.6 g) was chromatographed on silica gel (843 g) layered with basic alumina (468 g), eluting with 40% dichloromethane in hexanes to give bis[(1-(4-(tert-butyl)naphthalen-2-yl)-1′-yl)-8-isobutylbenzo[4,5]thieno[2,3-c]pyridin-2-yl]-(3,7-diethylnonane-4,6-dionato-k₂O,O′)iridium(III).

Synthesis of Inventive Example Compound 2

8-Isobutyl-1-(naphthalen-2-yl)benzo[4,5]thieno[2,3-c]pyridine (2.40 g, 6.53 mmol, 2.2 equiv) and iridium(III) chloride tetrahydrate (1.1 g, 2.97 mmol, 1.0 equiv) were charged to 40 mL reaction vial. 2-Ethoxyethanol (15 mL) and DIUF water (5 mL) were added and the reaction mixture stirred at 90° C. for about 60 hours. ¹H-NMR analysis indicated complete consumption of the starting ligand. The mixture was cooled to room temperature and diluted with DIUF water (5 mL). The solids were filtered and washed with methanol (20 mL) to give di-μ-chloro-tetrakis[1-(naphthalen-2-yl)-3′-yl)-8-isobutyl-benzo[4,5]thieno [2,3-c]pyridin-2-yl)]-diiridium(III) (1.42 g, 52% yield) as an orange solid.

A mixture of 3,7-diethylnonane-4,6-dione (1.180 g, 5.56 mmol, 8 equiv), crude di-μ-chloro-tetrakis[1-(naphthalen-2-yl)-3′-yl)-8-isobutyl-benzo[4,5]thieno [2,3-c]pyridin-2-yl)]-diiridium(III) (1.39 g, 0.722 mmol, 1.0 equiv), dichloromethane (1 mL) and methanol (25 mL) were charged to a 40 mL vial. Powdered potassium carbonate (1.152 g, 8.34 mmol, 12 equiv) was added and the mixture sparged with nitrogen for 5 minutes. After heating at 45° C. overnight, the reaction was cooled to room temperature and diluted with DIUF water (50 mL). After stirring for 10 minutes, the red-orange solid was filtered, washed with water (20 mL), then methanol (100 mL) and dried under vacuum, The solid was dissolved in dichloromethane (200 mL) and dry-loaded onto Celite (50 g). The product was chromatographed on basic alumina to afford bis[(1-(naphthalen-2-yl)-3′-yl)-8-isobutyl-benzo[4,5]thieno[2,3-c]pyridin-2-yl)]-(3,7-diethyl-4,6-nonanedionato-κ₂O,O′) iridium(III) (0.705 g, 97.2% purity, 43% yield) as a red-orange solid.

Synthesis of Comparative Example 1 Compound

A suspension of 8-isobutyl-1-(naphthalen-1-yl)benzo[4,5]thieno[2,3-c]pyridine (1.695 g, 4.61 mmol, 2.0 equiv) in 2-ethoxyethanol (12 mL) and DIUF water (4 mL) was sparged with nitrogen for 10 minutes. Iridium(III) chloride hydrate (0.73 g, 2.31 mmol, 1.0 equiv) was added, and the reaction mixture heated at 100° C. for 18 horns. The reaction was stopped and cooled to room temperature. The resulting red solid was filtered and washed with methanol (3×5 mL) to give the crude presumed intermediate di-μ-chloro-tetrakis[1-(naphthalen-1-yl)-2′-yl)-8-isobutyl-benzo[4.5] thieno[2,3-c]pyridin-1-yl)]-diiridium(III) (est. 1.153 mmol, wet) as a red solid.

Next, crude di-μ-chloro-tetrakis[1-(naphthalen-1-yl)-2′-yl)-8-isobutyl-benzo[4.5]thieno [2,3-c]pyridin-1-yl)]-diiridium(III) (est. 1.153 mmol, 1.0 equiv) was suspended in methanol (12 mL) and dichloromethane (1 mL). 3,7-Diethylnonane-4,6-dione (0.98 g, 4.61 mmol, 4.0 equiv) and powdered potassium carbonate (0.96 g, 6.92 mmol, 6.0 equiv) were added and the reaction mixture heated at 50° C. for 2 hours to form a new red suspension. The reaction was cooled to room temperature and diluted with water (10 mL). The solid was filtered and washed with water (2×3 mL) and methanol (3×1 mL). The red solid was purified on silica gel column eluted with a gradient of 0 to 50% dichloromethane in heptanes to give bis[(1-(naphthalen-1-yl)-2′-yl)-8-isobutyl-benzo[4,5]thieno[2,3-c]pyridin-1-yl)]-(3,7-diethyl-4,6-nonanedionato-k₂O,O′) iridium(III).

A photoluminescence (PL) spectra of compounds of the Inventive Example 1, Inventive Example 2, and the Comparative Example 1 were taken in 2-methylTHF solution at room temperature and the data are shown in the plot in FIG. 3. The PL intensities are normalized to the maximum of the first emission peaks. Both the Inventive Example 1 and the Comparative Example 1 show saturated red color. Compared to the Comparative Example 1, the Inventive Example 1 shows much narrower emission. It can be seen that the intensity of the second PL peak of the Inventive Example 1 is lower than that of the Comparative Example 1. The saturated emission color, narrower emission spectrum, more specifically the lower contribution from the second emission peak offers improved device performance, such as high electroluminescence efficiency and lower power consumption.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

1. A compound comprising a ligand L_(A) of Formula II,

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V,

 where indicated by “

”; each of X⁹ to X¹² is C; Z is selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form an aromatic ring; the ligand L_(A) is complexed to a metal M through the two indicated dashed lines; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.
 2. The compound of claim 1, wherein each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
 3. The compound of claim 1, wherein each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
 4. The compound of claim 1, wherein ring B is a 6-membered, carbocyclic ring.
 5. The compound of claim 1, wherein ring B is a 6-membered, heterocyclic ring.
 6. The compound of claim 1, wherein ring B is a 5-membered, heterocyclic ring.
 7. The compound of claim 1, wherein ring B is a 5-membered, carbocyclic ring.
 8. The compound of claim 1, wherein Z for each occurrence is independently O or S.
 9. The compound of claim 1, wherein at least one R^(B) in each formula is independently an alkyl or cycloalkyl group.
 10. The compound of claim 1, wherein the ligand L_(A) is selected from the group consisting of the following structures:


11. The compound of claim 1, wherein the metal M is Ir.
 12. The compound of claim 1, wherein the compound comprises the ligand L_(A) selected from the group consisting of:

wherein each of R^(B) can be the same or different, each of R^(C) can be the same or different, and R^(B) and R^(C) for each occurrence is independently selected from deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
 13. The compound of claim 1, wherein the compound has a formula of M(L_(A))_(p)(L_(B))_(q)(L_(C))_(r) wherein L_(B) and L_(C) are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
 14. The compound of claim 13, wherein L_(B) and L_(C) are each independently selected from the group consisting of:

wherein: each Y¹ to Y¹³ are independently selected from the group consisting of carbon and nitrogen; Y′ is selected from the group consisting of BR_(e), NR_(e), PR_(e), O, S, Se, C═O, S═O, SO₂, CR_(e)R_(f), SiR_(e)R_(f), and GeR_(e)R_(f); R_(e) and R_(f) can be fused or joined to form a ring; each R_(a), R_(b), R_(c), and R_(d) independently represent zero, mono, or up to a maximum allowed substitution to its associated ring; each of R_(a), R_(b), R_(c), R_(d), R_(e) and R_(f) is independently a hydrogen or a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) can be fused or joined to form a ring or form a multidentate ligand.
 15. The compound of claim 13, wherein M is Ir, p is 2, q is 0, r is 1, and L_(C) is

and wherein each of R_(a), R_(b), and R_(c) is independently a hydrogen or a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
 16. The compound of claim 1, wherein L_(A) is selected from the group consisting of:

wherein R_(B) has the same meaning as R^(B); and wherein R_(C) has the same meaning as R^(C).
 17. An organic light emitting device (OLED) comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound composing a ligand L_(A) of Formula II,

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V,

 where indicated by “

”; each of X⁹ to X¹² is C; Z is selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form an aromatic ring; the ligand L_(A) is complexed to a metal M through the two indicated dashed lines; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.
 18. The OLED of claim 17, wherein the organic layer further comprises a host, and the host is a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
 19. The OLED of claim 17, wherein The host can be, but is not limited to, a specific compound selected from the Host Group consisting of the group consisting of

and combinations thereof.
 20. A consumer product comprising an organic light emitting device (OLED) comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a ligand L_(A) of Formula II,

wherein: ring B is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; X¹ to X⁴ are each independently selected from the group consisting of C and CR; at least one pair of adjacent X¹ to X⁴ are each C and fused to a structure of Formula V,

 where indicated by “

”; each of X⁹ to X¹² is C; Z is selected from the group consisting of O, S, Se, NR′, CR′R″, SiR′R″, and GeR′R″; R^(B) and R^(C) each independently represents zero, mono, or up to a maximum allowed substitutions to its associated ring; each of R^(B), R^(C), R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and two substituents can be joined or fused to form an aromatic ring; the ligand L_(A) is complexed to a metal M through the two indicated dashed lines; and the ligand L_(A) can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand, wherein the consumer product is selected from the group consisting of a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display (a display that is less than 2 inches diagonal), a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign. 